Fungicidal pyrazoles

ABSTRACT

Disclosed are compounds of Formula 1 and Formula 1A including all stereoisomers, N-oxides, and salts thereof, 
                         
wherein
         Q 1 , Q 2 , R 1 , R 2 , R 4 , R 5  and X are as defined in the disclosure.
 
Also disclosed are compositions containing the compounds of Formula 1 or Formula 1A and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain pyrazoles, their N-oxides, salts andcompositions, and methods of their use as fungicides.

BACKGROUND OF THE INVENTION

The control of plant diseases caused by fungal plant pathogens isextremely important in achieving high crop efficiency. Plant diseasedamage to ornamental, vegetable, field, cereal, and fruit crops cancause significant reduction in productivity and thereby result inincreased costs to the consumer. Many products are commerciallyavailable for these purposes, but the need continues for new compoundswhich are more effective, less costly, less toxic, environmentally saferor have different sites of action.

PCT Patent Publication WO 2009/007098 A1 discloses certain pyrazolederivatives as fungicides.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allstereoisomers), N-oxides, and salts thereof, agricultural compositionscontaining them and their use as fungicides:

wherein

-   -   Q¹ is a phenyl ring substituted with 1 to 5 substituents        independently selected from R^(3a);    -   Q² is a phenyl ring substituted with 1 to 5 substituents        independently selected from R^(3a); or a 5- to 6-membered fully        unsaturated heterocyclic ring, each ring containing ring members        selected from carbon atoms and 1 to 3 heteroatoms independently        selected from up to 2 O, up to 2 S and up to 3 N atoms, wherein        up to 2 carbon ring members are independently selected from        C(═O) and C(═S), each ring optionally substituted with up to 5        substituents independently selected from R^(3a) on carbon atom        ring members and R^(3b) on nitrogen atom ring members;    -   R¹ is C₁-C₂ alkyl, halomethyl, cyanomethyl or cyclopropyl;    -   R² is H, halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl, C₂-C₄        alkynyl, C₁-C₂ haloalkyl, C₂-C₃ cyanoalkyl, C₁-C₂ hydroxyalkyl,        cyclopropyl, halocyclopropyl, C₂-C₃ alkoxyalkyl, C₁-C₂        alkylthio, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy;    -   each R^(3a) is independently halogen, cyano, hydroxy, nitro,        amino, C₁-C₃ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₃        haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₆        alkylcycloalkyl, C₄-C₆ cycloalkylalkyl, C₁-C₃ alkylthio, C₁-C₃        haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl,        C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₃ alkoxy,        C₁-C₃ haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃ alkylsulfonyloxy,        C₁-C₃ haloalkylsulfonyloxy, C₂-C₄ alkylcarbonyloxy, C₂-C₄        alkylcarbonyl, C₁-C₃ alkylamino, C₂-C₄ dialkylamino, C₂-C₄        alkylcarbonylamino, —CH(═O), —NHCH(═O), —SF₅, —SC≡N or —U—V-T;    -   each R^(3b) is independently cyano, C₁-C₃ alkyl, C₂-C₄ alkenyl,        C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₂-C₄ alkoxyalkyl, C₂-C₄        alkylaminoalkyl, C₃-C₄ dialkylaminoalkyl, C₁-C₃ alkoxy, C₂-C₄        alkylcarbonyl or C₂-C₄ alkoxycarbonyl;    -   R⁴ is halogen, —OR⁷ or —SC≡N;    -   R⁵ is H or C₁-C₄ alkyl;    -   R⁷ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆        alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ cyanoalkyl, C₂-C₆ alkoxyalkyl,        —CH(═O), —S(═O)₂OM¹ or —C(═W)R⁹;    -   R⁹ is C₁-C₆ alkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylaminoalkyl,        C₃-C₆ dialkylaminoalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ alkoxy or        C₁-C₆ alkylthio;    -   each U is independently O, S(═O)_(n), N(R¹⁰) or a direct bond;    -   each V is independently C₁-C₆ alkylene, C₂-C₆ alkenylene, C₃-C₆        alkynylene, C₃-C₆ cycloalkylene or C₃-C₆ cycloalkenylene,        wherein up to 3 carbon atoms are independently selected from        C(═O), each optionally substituted with up to 5 substituents        independently selected from halogen, cyano, nitro, hydroxy,        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy;    -   each T is independently cyano, N(R^(11a)) (R^(11b)), OR¹² or        S(═O)_(n)R¹²;    -   each R¹⁰ is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl,        C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈        cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈        cycloalkoxy(thiocarbonyl);    -   each R^(11a) and R^(11b) is independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or    -   a pair of R^(11a) and R^(11b) are taken together with the        nitrogen atom to which they are attached to form a form a 3- to        6-membered heterocyclic ring, the ring optionally substituted        with up to 5 substituents independently selected from R¹³;    -   each R¹² is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl,        C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl);    -   each R¹³ is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl        or C₁-C₆ alkoxy;    -   W is O or S;    -   M¹ is K, Na or Li; and    -   each n is independently 0, 1 or 2;    -   provided that when Q² is a phenyl ring which is not substituted        with R^(3a) at either ortho position, then Q¹ is substituted by        at least one R^(3a) at an ortho position.

This invention is also directed to compounds of Formula 1A (includingall stereoisomers), N-oxides, and salts thereof, agriculturalcompositions containing them and their use as fungicides:

wherein

-   -   Q¹ is a phenyl ring substituted with 1 to 5 substituents        independently selected from R^(3a);    -   Q² is a phenyl ring substituted with 1 to 5 substituents        independently selected from R^(3a); or a 5- to 6-membered fully        unsaturated heterocyclic ring, each ring containing ring members        selected from carbon atoms and 1 to 3 heteroatoms independently        selected from up to 2 O, up to 2 S and up to 3 N atoms, wherein        up to 2 carbon ring members are independently selected from        C(═O) and C(═S), each ring optionally substituted with up to 5        substituents independently selected from R^(3a) on carbon atom        ring members and R^(3b) on nitrogen atom ring members;    -   X is O, S(O)_(m), N(R⁶) or C(═O);    -   R¹ is C₁-C₂ alkyl, halomethyl, cyanomethyl or cyclopropyl;    -   R² is H, halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl, C₂-C₄        alkynyl, C₁-C₂ haloalkyl, C₂-C₃ cyanoalkyl, C₁-C₂ hydroxyalkyl,        cyclopropyl, halocyclopropyl, C₂-C₃ alkoxyalkyl, C₁-C₂        alkylthio, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy;    -   each R^(3a) is independently halogen, cyano, hydroxy, nitro,        amino, C₁-C₃ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₃        haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₆        alkylcycloalkyl, C₄-C₆ cycloalkylalkyl, C₁-C₃ alkylthio, C₁-C₃        haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl,        C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₃ alkoxy,        C₁-C₃ haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃ alkylsulfonyloxy,        C₁-C₃ haloalkylsulfonyloxy, C₂-C₄ alkylcarbonyloxy, C₂-C₄        alkylcarbonyl, C₁-C₃ alkylamino, C₂-C₄ dialkylamino, C₂-C₄        alkylcarbonylamino, —CH(═O), —NHCH(═O), —SF₅, —SC≡N or —U—V-T;    -   each R^(3b) is independently cyano, C₁-C₃ alkyl, C₂-C₄ alkenyl,        C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₂-C₄ alkoxyalkyl, C₂-C₄        alkylaminoalkyl, C₃-C₄ dialkylaminoalkyl, C₁-C₃ alkoxy, C₂-C₄        alkylcarbonyl or C₂-C₄ alkoxycarbonyl;    -   R⁶ is H, hydroxy, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl,        C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆        cyanoalkyl, NH₂, —CH(═O), —OR⁷, —OS(═O)₂M¹, —S(═O)_(n)R⁸ or        —C(═W)R⁹;    -   R⁷ is C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆        alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ cyanoalkyl, C₂-C₆ alkoxyalkyl,        —CH(═O), —S(═O)₂OM¹ or —C(═W)R⁹;    -   R⁸ is C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   R⁹ is C₁-C₆ alkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylaminoalkyl,        C₃-C₆ dialkylaminoalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ alkoxy or        C₁-C₆ alkylthio;    -   each U is independently O, S(═O)_(n), N(R¹⁰) or a direct bond;    -   each V is independently C₁-C₆ alkylene, C₂-C₆ alkenylene, C₃-C₆        alkynylene, C₃-C₆ cycloalkylene or C₃-C₆ cycloalkenylene,        wherein up to 3 carbon atoms are independently selected from        C(═O), each optionally substituted with up to 5 substituents        independently selected from halogen, cyano, nitro, hydroxy,        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy;    -   each T is independently cyano, N(R^(11a)) (R^(11b)), OR¹² or        S(═O)_(n)R¹²;    -   each R¹⁰ is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl,        C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈        cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈        cycloalkoxy(thiocarbonyl);    -   each R^(11a) and R^(11b) is independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or    -   a pair of R^(11a) and R^(11b) are taken together with the        nitrogen atom to which they are attached to form a form a 3- to        6-membered heterocyclic ring, the ring optionally substituted        with up to 5 substituents independently selected from R¹³;    -   each R¹² is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl,        C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl);    -   each R¹³ is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl        or C₁-C₆ alkoxy;    -   W is O or S;    -   M¹ is K, Na or Li;    -   m is 0, 1 or 2; and    -   each n is independently 0, 1 or 2;

provided that:

-   -   (a) when Q² is a phenyl ring which is not substituted with        R^(3a) at either ortho position, then Q¹ is substituted by at        least one R^(3a) at an ortho position; and    -   (b) the compound is other than        1-[2-[4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl]phenyl]ethanone.

More particularly, this invention pertains to a compound selected fromcompounds of Formula 1 (including all stereoisomers), an N-oxide or asalt thereof; or a compound selected from compounds of Formula 1A(including all stereoisomers), an N-oxide or a salt thereof.

This invention also relates to a fungicidal composition comprising (a) acompound of the invention (i.e. in a fungicidally effective amount); and(b) at least one additional component selected from the group consistingof surfactants, solid diluents and liquid diluents.

This invention also relates to a fungicidal composition comprising (a) acompound of the invention; and (b) at least one other fungicide (e.g.,at least one other fungicide having a different site of action).

This invention further relates to a method for controlling plantdiseases caused by fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of the invention (e.g., as a composition describedherein).

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such composition, mixture, process, method,article, or apparatus.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method or apparatus that includes materials, steps,features, components, or elements, in addition to those literallydisclosed, provided that these additional materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of:”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, “plant” includesmembers of Kingdom Plantae, particularly seed plants (Spermatopsida), atall life stages, including young plants (e.g., germinating seedsdeveloping into seedlings) and mature, reproductive stages (e.g., plantsproducing flowers and seeds). Portions of plants include geotropicmembers typically growing beneath the surface of the growing medium(e.g., soil), such as roots, tubers, bulbs and corms, and also membersgrowing above the growing medium, such as foliage (including stems andleaves), flowers, fruits and seeds.

As referred to herein, the term “seedling”, used either alone or in acombination of words means a young plant developing from the embryo of aseed.

As referred to herein, the term “broadleaf” used either alone or inwords such as “broadleaf crop” means dicot or dicotyledon, a term usedto describe a group of angiosperms characterized by embryos having twocotyledons.

As used herein, the term “alkylating agent” refers to a chemicalcompound in which a carbon-containing radical is bound through a carbonatom to a leaving group such as halide or sulfonate, which isdisplaceable by bonding of a nucleophile to said carbon atom. Unlessotherwise indicated, the term “alkylating agent” does not limit thecarbon-containing radical to alkyl; the carbon-containing radicals inalkylating agents include the variety of carbon-bound substituentradicals specified, for example, for R¹ and Q¹.

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl such as methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkylene”denotes a straight-chain or branched alkanediyl. Examples of “alkylene”include CH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃), and the differentbutylene, pentylene or hexylene isomers. “Alkenylene” denotes astraight-chain or branched alkenediyl containing one olefinic bond.Examples of “alkenylene” include CH═CH, CH₂CH═CH and CH═C(CH₃).“Alkynylene” denotes a straight-chain or branched alkynediyl containingone triple bond. Examples of “alkynylene” include CH₂C≡C, C≡CCH₂, andthe different butynylene, pentynylene or hexynylene isomers.

The term “cycloalkyl” denotes a saturated carbocyclic ring consisting of3 to 7 carbon atoms linked to one another by single bonds. Examples of“cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl. The term “alkylcycloalkyl” denotes alkyl substitution on acycloalkyl moiety and includes, for example, ethylcyclopropyl,i-propylcyclopropyl and methylcyclopentyl. The term “cycloalkylalkyl”denotes cycloalkyl substitution on an alkyl moiety. Examples of“cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and othercycloalkyl moieties bonded to straight-chain or branched alkyl groups.The term “cycloalkylcycloalkyl” denotes cycloalkyl substitution onanother cycloalkyl ring, wherein each cycloalkyl ring independently hasfrom 3 to 7 carbon atom ring members. Examples of cycloalkylcycloalkylinclude cyclopropylcyclopropyl (such as 1,1′-bicyclopropyl-1-yl,1,1′-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as1,1′-bicyclohexyl-1-yl), and the different cis- andtrans-cycloalkylcycloalkyl isomers, (such as(1R,2S)-1,1′-bicyclopropyl-2-yl and (1R,2R)-1,1′-bicyclopropyl-2-yl).The term “cycloalkoxy” denotes cycloalkyl attached to and linked throughan oxygen atom including, for example, cyclopentyloxy and cyclohexyloxy.“Cycloalkylcarbonyl” denotes cycloalkyl bonded to a C(═O) groupincluding, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. Theterm “cycloalkoxycarbonyl” means cycloalkoxy bonded to a C(═O) group,for example, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. The term“cycloalkylene” denotes a cycloalkanediyl ring. Examples of“cycloalkylene” include cyclopropylene, cyclobutylene, cyclopentyleneand cyclohexylene. The term “cycloalkenylene” denotes a cycloalkenediylring containing one olefinic bond. Examples of “cycloalkenylene” includecyclopropylene, cyclobutylene and cyclopentylene.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,i-propyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkylamino” includes an NH radical substituted with straight-chain orbranched alkyl. Examples of “alkylamino” include CH₃CH₂NH, CH₃CH₂CH₂NHand (CH₃)₂CHCH₂NH. “Alkylthio” includes branched or straight-chainalkylthio moieties such as methylthio, ethylthio, and the differentpropylthio, butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl”includes both enantiomers of an alkylsulfinyl group. Examples of“alkylsulfinyl” include CH₃S(═O), CH₃CH₂S(═O), CH₃CH₂CH₂S(═O),(CH₃)₂CHS(═O), and the different ethylsulfinyl or propylsulfinylisomers. Examples of “alkylsulfonyl” include CH₃S(═O)₂, CH₃CH₂S(═O)₂,CH₃CH₂CH₂S(═O)₂, (CH₃)₂CHS(═O)₂, and the different ethylsulfonyl orpropylsulfonyl isomers. The term “alkylsulfonyloxy” denotesalkylsulfonyl attached to and linked through an oxygen atom. Examples of“alkylsulfonyloxy” include CH₃S(═O)₂O and CH₃CH₂S(═O)₂O.

“Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of“alkoxyalkyl” include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂and CH₃CH₂OCH₂CH₂. “Alkylthioalkyl” denotes alkylthio substitution onalkyl. Examples of “alkylthioalkyl” include CH₃SCH₂, CH₃SCH₂CH₂,CH₃CH₂SCH₂, CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂. “Alkylaminoalkyl”denotes alkylamino substitution on alkyl. Examples of “alkylaminoalkyl”include CH₃ NHCH₂, CH₃ NHCH₂CH₂, CH₃CH₂NHCH₂, CH₃CH₂CH₂CH₂NHCH₂ andCH₃CH₂NHCH₂CH₂. Examples of “dialkylaminoalkyl” include (CH₃CH)₂NCH₂ andCH₃CH₂(CH₃)NCH₂CH₂.

“Cyanoalkyl” denotes an alkyl group substituted with one cyano group.Examples of “cyanoalkyl” include NCCH₂, (also referred to herein as“cyanomethyl”) NCCH₂CH₂ and CH₃CH(CN)CH₂. “Hydroxyalkyl” denotes analkyl group substituted with one hydroxy group. Examples of“hydroxyalkyl” include HOCH₂, (also referred to herein as“hydroxymethyl”) and HOCH₂CH₂.

“Alkylcarbonyl” denotes a straight-chain or branched alkyl group bondedto a C(═O) moiety. Examples of “alkylcarbonyl” include CH₃C(═O),CH₃CH₂CH₂C(═O) and (CH₃)₂CHC(═O). Examples of “alkoxycarbonyl” includeCH₃C(═O), CH₃CH₂OC(═O), CH₃CH₂CH₂C(═O), (CH₃)₂CHOC(═O) and the differentpentoxy- or hexoxycarbonyl isomers. The term “alkylcarbonyloxy” denotesstraight-chain or branched alkyl bonded to a C(═O)O moiety. Examples of“alkylcarbonyloxy” include CH₃CH₂C(═O)O and (CH₃)₂CHC(═O)O.“Alkoxy(thiocarbonyl)” denotes a straight-chain or branched alkoxy groupbonded to a C(═S) moiety. Examples of “alkoxy(thiocarbonyl)” includeCH₃C(═S), CH₃CH₂CH₂C(═S) and (CH₃)₂CHOC(═S). “(Alkylthio)carbonyl”denotes a straight-chain or branched alkylthio group bonded to a C(═O)moiety. Examples of “(alkylthio)carbonyl” include CH₃SC(═O),CH₃CH₂CH₂SC(═O) and (CH₃)₂CHSC(═O). The term “alkylcarbonylamino”denotes alkyl bonded to a C(═O)NH moiety. Examples of“alkylcarbonylamino” include CH₃CH₂C(═O)NH and CH₃CH₂CH₂C(═O)NH.

The term “halogen”, either alone or in compound words such as“halomethyl”, “haloalkyl”, or when used in descriptions such as “alkylsubstituted with halogen” includes fluorine, chlorine, bromine oriodine. Further, when used in compound words such as “halomethyl”,“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” said methyl or alkyl may be partially or fully substitutedwith halogen atoms which may be the same or different. Examples of“haloalkyl” or “alkyl substituted with halogen” include F₃C, ClCH₂,CF₃CH₂ and CF₃CCl₂. The terms “haloalkoxy”, “haloalkylthio”,“haloalkylsulfinyl” “haloalkylsulfonyl” and “halocycloalkyl” are definedanalogously to the term “haloalkyl”. Examples of “haloalkoxy” includeCF₃O, CCl₃CH₂O, F₂CHCH₂CH₂O and CF₃CH₂O. Examples of “haloalkylthio”include CF₃S, CCl₃S and CF₃CH₂S. Examples of “haloalkylsulfinyl” includeCF₃S(═O), CCl₃S(═O), CF₃CH₂S(═O) and CF₃CF₂S(═O). Examples of“haloalkylsulfonyl” include CF₃S(═O)₂, CCl₃S(═O)₂, CF₃CH₂S(═O)₂ andCF₃CF₂S(═O)₂. Examples of “halocycloalkyl” include chlorocyclopropyl,fluorocyclobutyl and chlorocyclohexyl.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 8. Forexample, C₁-C₄ alkylsulfonyl designates methylsulfonyl throughbutylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyldesignates, for example, CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C₄ alkoxyalkyldesignates the various isomers of an alkyl group substituted with analkoxy group containing a total of four carbon atoms, examples includingCH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

The term “unsubstituted” in connection with a group such as a ring meansthe group does not have any substituents other than its one or moreattachments to the remainder of Formula 1 or Formula 1A. The term“optionally substituted” means that the number of substituents can bezero. Unless otherwise indicated, optionally substituted groups may besubstituted with as many optional substituents as can be accommodated byreplacing a hydrogen atom with a non-hydrogen substituent on anyavailable carbon or nitrogen atom. Commonly, the number of optionalsubstituents (when present) range from 1 to 3. As used herein, the term“optionally substituted” is used interchangeably with the phrase“substituted or unsubstituted” or with the term “(un)substituted.”

The number of optional substituents may be restricted by an expressedlimitation. For example, the phrase “optionally substituted with up to 3substituents independently selected from R^(3a) on carbon atom ringmembers” means that 0, 1, 2 or 3 substituents can be present (if thenumber of potential connection points allows). Similarly, the phrase“optionally substituted with up to 5 substituents independently selectedfrom R^(3a) on carbon atom ring members” means that 0, 1, 2, 3, 4 or 5substituents can be present if the number of available connection pointsallows. When a range specified for the number of substituents (e.g., rbeing an integer from 0 to 4 in Exhibit 1) exceeds the number ofpositions available for substituents on a ring (e.g., only 2 positionsare available for (R^(v))_(r) on A-11 in Exhibit 1), the actual higherend of the range is recognized to be the number of available positions.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents (e.g., (R^(v))_(r) wherein r is 1, 2, 3 or4 in Exhibit 1). When a variable group is shown to be optionallyattached, for example (R^(v))_(r) wherein r may be 0, then hydrogen maybe at the position even if not recited in the variable group definition.When one or more positions on a group are said to be “not substituted”or “unsubstituted”, then hydrogen atoms are attached to take up any freevalency.

Unless otherwise indicated, a “ring” as a component of Formula 1 orFormula 1A (e.g., Q²) is carbocyclic (e.g., phenyl) or heterocyclic(e.g., pyridinyl). The term “ring member” refers to an atom (e.g., C, O,N or S) or other moiety (e.g., C(═O) or C(═S)) forming the backbone of aring.

The term “nonaromatic” includes rings that are fully saturated as wellas partially or fully unsaturated, provided that none of the rings arearomatic. The term “aromatic” indicates that each of the ring atoms of afully unsaturated ring is essentially in the same plane and has ap-orbital perpendicular to the ring plane, and that (4n+2) π electrons,where n is a positive integer, are associated with the ring to complywith Hückel's rule. The term “fully unsaturated heterocyclic ring”includes both aromatic and nonaromatic fully unsaturated heterocycles.

The terms “carbocyclic ring” or “carbocycle” denote a ring wherein theatoms forming the ring backbone are selected only from carbon. When afully unsaturated carbocyclic ring satisfies Hückel's rule, then saidring is also called an “aromatic carbocyclic ring”. The term “saturatedcarbocyclic ring” refers to a ring having a backbone consisting ofcarbon atoms linked to one another by single bonds; unless otherwisespecified, the remaining carbon valences are occupied by hydrogen atoms.

The terms “heterocyclic ring” or “heterocycle” denote rings in which atleast one atom forming the ring backbone is not carbon (e.g., N, O orS). Typically a heterocyclic ring contains no more than 3 N atoms, nomore than 2 O atoms and no more than 2S atoms. Unless otherwiseindicated, a heterocyclic ring can be a saturated, partially unsaturatedor fully unsaturated ring. When a fully unsaturated heterocyclic ringsatisfies Hückel's rule, then said ring is also called a “heteroaromaticring” or “aromatic heterocyclic ring”. Unless otherwise indicated,heterocyclic rings can be attached through any available carbon ornitrogen by replacement of a hydrogen on said carbon or nitrogen.

In the context of the present invention, when an instance of Q¹ or Q²comprises a phenyl or a 6-membered fully unsaturated heterocyclic ring,the ortho, meta and para positions of each ring is relative to theconnection of the ring to the remainder of Formula 1.

As noted above, Q¹ and Q² can be, inter alia, phenyl optionallysubstituted with 1 to 5 substituents independently selected from R^(3a).In the circumstances when an instance of Q¹ or Q² comprises a phenylring substituted with 4 or less substituents independently selected fromR^(3a), then hydrogen atoms are attached to take up any free valency.

As noted above, Q² attached to Formula 1 or Formula 1A is, inter alia, a5- to 6-membered fully unsaturated heterocyclic ring, each ringcontaining ring members selected from carbon atoms and up to 3heteroatoms independently selected from up to 2 O, up to 2 S and up to 3N atoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S), each ring optionally substituted with upto 5 substituents independently selected from any substituent as definedin the Summary of the Invention for Q² (i.e. R^(3a) on carbon atom ringmembers and R^(3b) on nitrogen atom ring members). As the substituentsare optional, 0 to 5 substituents may be present, limited only by thenumber of available points of attachment. In this definition the ringmembers selected from up to 2 O, up to 2 S and up to 3 N atoms areoptional, provided at least one ring member is not carbon (e.g., N, O orS). The nitrogen atom ring members may be oxidized as N-oxides, becausecompounds relating to Formula 1 or Formula 1A also include N-oxidederivatives. The up to 2 carbon atom ring members selected from C(═O)and C(═S) are in addition to the up to 3 heteroatoms selected from up to2 O, up to 2 S and up to 3 N atoms. Examples of a 5- to 6-membered fullyunsaturated heterocyclic ring include the rings A-1 through A-31illustrated in Exhibit 1. The variable R^(v), in Exhibit 1, is anysubstituent as defined in the Summary of the Invention for Q² (i.e.R^(3a) on carbon atom ring members and R^(3b) on nitrogen atom ringmembers) and r is an integer from 0 to 4, limited by the number ofavailable positions on each depicted ring.

Although R^(v) groups are shown in the structures A-1 through A-31, itis noted that they do not need to be present since they are optionalsubstituents. The nitrogen atoms that require substitution to fill theirvalence are substituted with H or R^(v). Note that when the attachmentpoint between (R^(v))^(r) and the depicted ring is illustrated asfloating, (R^(v))^(r) can be attached to any available carbon ornitrogen atom of the depicted ring. Note that when the attachment pointof the depicted ring to the remainder of Formula 1 or 1A is illustratedas floating, the ring can be attached to the remainder of Formula 1 or1A through any available carbon or nitrogen of the depicted ring byreplacement of a hydrogen atom.

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic heterocyclic rings; for extensive reviews seethe eight volume set of Comprehensive Heterocyclic Chemistry, A. R.Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A.R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, PergamonPress, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. The compounds of the invention may be present as amixture of stereoisomers, individual stereoisomers or as an opticallyactive form. Of note are atropisomers, which are stereoisomericconformations of a molecule that occur when rotation about a single bondis restricted such that interconversion is slow enough to allowseparation. Restricted rotation of one or more bonds is a result ofsteric interaction with other parts of the molecule. In the presentinvention, compounds of Formula 1 and Formula 1A can exhibitatropisomerism when the energy barrier to free rotation around a singleunsymmetrical bond is sufficiently high that separation of isomers ispossible. Atropisomerism is defined to exist where the isomers have ahalf-life of at least 1000 seconds, which is a free energy barrier of atleast about 22.3 kcal mol⁻¹ at about 20° C. (Oki, Topics inStereochemistry, Vol. 14, John Wiley & Sons, Inc., 1983). One skilled inthe art will appreciate that one atropisomer may be more active and/ormay exhibit beneficial effects when enriched relative to the otheratropisomer or when separated from the other atropisomer. Additionally,the skilled artisan knows how to separate, enrich, and/or to selectivelyprepare said atropisomers. Further description of atropisomers can befound in March, Advanced Organic Chemistry, 101-102, 4^(th) Ed. 1992;Oki, Topics in Stereochemistry, Vol. 14, John Wiley & Sons, Inc., 1983and Gawronski et al, Chirality 2002, 14, 689-702. This inventionincludes compounds that are enriched compared to the racemic mixture inan atropisomer of Formula 1 or Formula 1A. Also included are theessentially pure atropisomers of compounds of Formula 1 or Formula 1A.

Also of note are enantiomers of Formula 1 and Formula 1A. For example,two possible enantiomers of Formula 1 are depicted below as Formula 1′and Formula 1″ wherein the chiral center is identified with an asterisk(*) and the substituents R⁴ and R⁵ are not identical.

Molecular depictions drawn herein follow standard conventions fordepicting stereochemistry. To indicate stereoconfiguration, bonds risingfrom the plane of the drawing and towards the viewer are denoted bysolid wedges wherein the broad end of the wedge is attached to the atomrising from the plane of the drawing towards the viewer. Bonds goingbelow the plane of the drawing and away from the viewer are denoted bydashed wedges wherein the narrow end of the wedge is attached to theatom further away from the viewer. Constant width lines indicate bondswith a direction opposite or neutral relative to bonds shown with solidor dashed wedges; constant width lines also depict bonds in molecules orparts of molecules in which no particular stereoconfiguration isintended to be specified.

This invention comprises racemic mixtures, for example, equal amounts ofthe enantiomers of Formulae 1′ and 1″. In addition, this inventionincludes compounds that are enriched compared to the racemic mixture inan enantiomer of Formula 1 or 1A. Also included are the essentially pureenantiomers of compounds of Formula 1 or 1A, for example, Formula 1′ andFormula 1″.

When enantiomerically enriched, one enantiomer is present in greateramounts than the other, and the extent of enrichment can be defined byan expression of enantiomeric excess (“ee”), which is defined as(2x−1)·100%, where x is the mole fraction of the dominant enantiomer inthe mixture (e.g., an ee of 20% corresponds to a 60:40 ratio ofenantiomers).

Of note are compositions of this invention having at least a 50%, or atleast a 75%, or at least a 90%, or at least a 94% enantiomeric excess ofan isomer. Of particular note are enantiomerically pure embodiments.

Compounds of Formula 1 or Formula 1A can comprise additional chiralcenters. For example, substituents such as R^(3a) may themselves containchiral centers.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 and Formula 1A are useful for control ofplant diseases caused by fungal plant pathogens (i.e. are agriculturallysuitable). The salts of the compounds of Formula 1 and Formula 1Ainclude acid-addition salts with inorganic or organic acids such ashydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic,butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic,tartaric, 4-toluenesulfonic or valeric acids.

Compounds selected from Formula 1 or Formula 1A, stereoisomers,N-oxides, and salts thereof, typically exist in more than one form,therefore Formula 1 and Formula 1A includes all crystalline andnon-crystalline forms of the compounds that Formula 1 and Formula 1Arepresents. Non-crystalline forms include embodiments which are solidssuch as waxes and gums as well as embodiments which are liquids such assolutions and melts. Crystalline forms include embodiments whichrepresent essentially a single crystal type and embodiments whichrepresent a mixture of polymorphs (i.e. different crystalline types).The term “polymorph” refers to a particular crystalline form of achemical compound that can crystallize in different crystalline forms,these forms having different arrangements and/or conformations of themolecules in the crystal lattice. Although polymorphs can have the samechemical composition, they can also differ in composition due thepresence or absence of co-crystallized water or other molecules, whichcan be weakly or strongly bound in the lattice. Polymorphs can differ insuch chemical, physical and biological properties as crystal shape,density, hardness, color, chemical stability, melting point,hygroscopicity, suspensibility, dissolution rate and biologicalavailability. One skilled in the art will appreciate that a polymorph ofa compound represented by Formula 1 or Formula 1A can exhibit beneficialeffects (e.g., suitability for preparation of useful formulations,improved biological performance) relative to another polymorph or amixture of polymorphs of the same compound represented by Formula 1 orFormula 1A. Preparation and isolation of a particular polymorph of acompound represented by Formula 1 or Formula 1A can be achieved bymethods known to those skilled in the art including, for example,crystallization using selected solvents and temperatures.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,Formula 1 includes stereoisomers, N-oxides and salts thereof, andreference to “a compound of Formula 1” includes the definitions ofsubstituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

Embodiment 1

-   -   A compound of Formula 1 wherein Q¹ is a phenyl ring substituted        with 1 to 3 substituents independently selected from R^(3a).

Embodiment 2

-   -   A compound of Embodiment 1 wherein Q¹ is a phenyl ring        substituted with 2 to 3 substituents independently selected from        R^(3a).

Embodiment 3

-   -   A compound of Embodiment 1 wherein Q¹ is a phenyl ring        substituted with 1 substituent independently selected from        R^(3a).

Embodiment 4

-   -   A compound of Embodiment 1 wherein Q¹ is a phenyl ring        substituted with 2 substituents independently selected from        R^(3a).

Embodiment 5

-   -   A compound of Embodiment 1 wherein Q¹ is a phenyl ring        substituted with 3 substituents selected from R^(3a).

Embodiment 6

-   -   A compound of Formula 1 or any one of Embodiments 1 through 5        wherein Q¹ is a phenyl ring substituted with at least one R^(3a)        substituent attached at an ortho position (relative to the        connection of the Q¹ ring to the remainder of Formula 1).

Embodiment 6a

-   -   A compound of Formula 1 or any one of Embodiments 1 through 6        wherein Q¹ is a phenyl ring substituted with two R^(3a)        substituents attached at an ortho position and the para position        (relative to the connection of the Q¹ ring to the remainder of        Formula 1).

Embodiment 6b

-   -   A compound of Formula 1 or any one of Embodiments 1 through 6        wherein Q¹ is a phenyl ring substituted with two R^(3a)        substituents attached at both ortho positions (relative to the        connection of the Q¹ ring to the remainder of Formula 1).

Embodiment 6c

-   -   A compound of Formula 1 or any one of Embodiments 1 through 6        wherein Q¹ is a phenyl ring substituted with three R^(3a)        substituents attached at both ortho positions and the para        position (relative to the connection of the Q¹ ring to the        remainder of Formula 1).

Embodiment 7

-   -   A compound of Formula 1 or any one of Embodiments 1 through 6c        wherein Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a); or a pyrazolyl, imidazolyl,        pyridinyl, pyridazinyl, pyrazinyl or pyrimidinyl ring, each ring        optionally substituted with up to 3 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members.

Embodiment 8

-   -   A compound of Embodiment 7 wherein Q² is a phenyl ring        substituted with 1 to 3 substituents independently selected from        R^(3a); or a pyrazolyl, imidazolyl or pyridinyl ring, each ring        optionally substituted with 1 to 3 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members.

Embodiment 9

-   -   A compound of Embodiment 8 wherein Q² is a phenyl ring        substituted with 1 to 3 substituents independently selected from        R^(3a).

Embodiment 9a

-   -   A compound of Embodiment 9 wherein Q² is a phenyl ring        substituted with 2 to 3 substituents independently selected from        R^(3a).

Embodiment 9b

-   -   A compound of Embodiment 9 wherein Q² is a phenyl ring        substituted with 1 substituent independently selected from        R^(3a).

Embodiment 9c

-   -   A compound of Embodiment 9 wherein Q² is a phenyl ring        substituted with 2 substituents independently selected from        R^(3a).

Embodiment 9d

-   -   A compound of Embodiment 9 wherein Q² is a phenyl ring        substituted with 3 substituents independently selected from        R^(3a).

Embodiment 9e

-   -   A compound of Formula 1 or any one of Embodiments 1 through 9        wherein Q² is a phenyl ring substituted with two R^(3a)        substituents attached at an ortho position and the para position        (relative to the connection of the Q² ring to the remainder of        Formula 1).

Embodiment 9f

-   -   A compound of Formula 1 or any one of Embodiments 1 through 9        wherein Q² is a phenyl ring substituted with two R^(3a)        substituents attached at both ortho positions (relative to the        connection of the Q² ring to the remainder of Formula 1).

Embodiment 9g

-   -   A compound of Formula 1 or any one of Embodiments 1 through 9        wherein Q² is a phenyl ring substituted with three R^(3a)        substituents attached at both ortho positions and the para        position (relative to the connection of the Q² ring to the        remainder of Formula 1).

Embodiment 10

-   -   A compound of Embodiment 8 wherein Q² is a pyridinyl ring        optionally substituted with up to 3 substituents independently        selected from R^(3a).

Embodiment 11

-   -   A compound of Embodiment 10 wherein Q² is a pyridinyl ring        substituted with 1 to 3 substituents independently selected from        R^(3a).

Embodiment 12

-   -   A compound of Formula 1 or any one of Embodiments 1 through 11        wherein when Q² is a 6-membered fully unsaturated heterocyclic        ring (e.g., pyridinyl, pyridazinyl, pyrazinyl or pyrimidinyl),        then Q² is substituted with at least one R^(3a) substituent        attached at an ortho position (relative to the connection of the        Q² ring to the remainder of Formula 1).

Embodiment 13

-   -   A compound of Formula 1 or any one of Embodiments 1 through 12        wherein when Q¹ and Q² are each a phenyl substituted with 1 to 3        substituents independently selected from R^(3a), then one ring        is substituted with 2 to 3 substituents and the ring is        substituted with 1 to 3 substituents.

Embodiment 14

-   -   A compound of Formula 1 or any one of Embodiments 1 through 12        wherein when Q¹ and Q² are each a phenyl ring substituted with 1        to 3 substituents independently selected from R^(3a), then one        ring is substituted with 2 to 3 substituents and the other ring        is substituted with 1 to 2 substituents.

Embodiment 14a

-   -   A compound of Formula 1 or any one of Embodiments 1 through 12        wherein when Q¹ and Q² are each a phenyl ring substituted with 1        to 3 substituents independently selected from R^(3a), then one        ring is substituted with 3 substituents and the other ring        substituted with 2 substituents.

Embodiment 14b

-   -   A compound of Formula 1 or any one of Embodiments 1 through 12        wherein Q¹ and Q² are both a phenyl ring substituted with 2        substituents independently selected from R^(3a).

Embodiment 15

-   -   A compound of Formula 1 or any one of Embodiments 1 through 14b        wherein R¹ is C₁-C₂ alkyl, —CH₂F, —CH₂Cl or cyclopropyl.        Embodiment 16    -   A compound of Embodiment 15 wherein R¹ is methyl, —CH₂F or        —CH₂Cl.

Embodiment 17

-   -   A compound of Embodiment 16 wherein R¹ is methyl.

Embodiment 18

-   -   A compound of Formula 1 or any one of Embodiments 1 through 17        wherein R² is H, halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl,        halomethyl, cyanomethyl, hydroxymethyl, C₂-C₃ alkoxyalkyl, C₁-C₂        alkoxy or C₁-C₂ haloalkoxy.

Embodiment 18a

-   -   A compound of Embodiment 18 wherein R² is halogen, cyano, C₁-C₂        alkyl, halomethyl, cyanomethyl, hydroxymethyl, C₁-C₂ alkoxy or        C₁-C₂ haloalkoxy.

Embodiment 18b

-   -   A compound of Embodiment 18a wherein R² is halogen, cyano, C₁-C₂        alkyl, halomethyl, cyanomethyl, hydroxymethyl or methoxy.

Embodiment 19

-   -   A compound of Embodiment 18b wherein R² is halogen, cyano,        methyl, halomethyl or methoxy.

Embodiment 20

-   -   A compound of Embodiment 19 wherein R² is Br, Cl, F, cyano,        methyl or methoxy.

Embodiment 20a

-   -   A compound of Embodiment 20 wherein R² is Br, Cl, methyl or        methoxy.

Embodiment 20b

-   -   A compound of Embodiment 20a wherein R² is Br, Cl or methoxy.

Embodiment 21

-   -   A compound of Embodiment 20a wherein R² is methyl.

Embodiment 22

-   -   A compound of Formula 1 or any one of Embodiments 1 through 21        wherein each R^(3a) is independently halogen, cyano, C₁-C₂        alkyl, C₁-C₂ haloalkyl, cyclopropyl, C₁-C₂ alkoxy, C₁-C₂        alkylthio, C₂-C₃ alkylcarbonyl or —U—V-T.

Embodiment 23

-   -   A compound of Embodiment 22 wherein each R^(3a) is independently        halogen, cyano, methyl, halomethyl, cyclopropyl, methoxy,        methylthio, methylcarbonyl or —U—V-T.

Embodiment 24

-   -   A compound of Embodiment 23 wherein each R^(3a) is independently        halogen, cyano, methyl, halomethyl or methoxy.

Embodiment 25

-   -   A compound of Embodiment 24 wherein each R^(3a) is independently        halogen, cyano or methoxy.

Embodiment 26

-   -   A compound of Embodiment 25 wherein each R^(3a) is independently        Br, Cl, F, cyano or methoxy.

Embodiment 27

-   -   A compound of Embodiment 26 wherein each R^(3a) is independently        Cl or F.

Embodiment 28

-   -   A compound of Formula 1 or any one of Embodiments 1 through 27        wherein each U is independently ON(R¹⁰) or a direct bond.

Embodiment 29

-   -   A compound of Embodiment 28 wherein each R¹⁰ is independently H        or methyl.

Embodiment 30

-   -   A compound of Embodiment 28 wherein each U is independently O,        NH or a direct bond.

Embodiment 31

-   -   A compound of Formula 1 or any one of Embodiments 1 through 30        wherein each V is independently C₁-C₄ alkylene, wherein up to 1        carbon atom is selected from C(═O).

Embodiment 32

-   -   A compound of Embodiment 31 wherein each V is independently        C₁-C₃ alkylene.

Embodiment 33

-   -   A compound of Formula 1 or any one of Embodiments 1 through 32        wherein each T is independently N(R^(11a))(R^(11b)) or OR¹².

Embodiment 34

-   -   A compound of Formula 1 or any one of Embodiments 1 through 33        wherein each R^(11a) and R^(11b) is independently H, C₁-C₆ alkyl        or C₁-C₆ haloalkyl.

Embodiment 35

-   -   A compound of Embodiment 34 wherein each R^(11a) and R^(11b) is        independently H or methyl.

Embodiment 36

-   -   A compound of Formula 1 or any one of Embodiments 1 through 35        wherein each R¹² is independently H, C₁-C₆ alkyl or C₁-C₆        haloalkyl.

Embodiment 37

-   -   A compound Embodiment 36 wherein each R¹² is independently H,        methyl or halomethyl.

Embodiment 38

-   -   A compound of Formula 1 or any one of Embodiments 1 through 37        wherein each R^(3b) is independently cyano, C₁-C₂ alkyl,        cyclopropyl or C₂-C₃ alkoxyalkyl.

Embodiment 39

-   -   A compound of Embodiment 38 wherein each R^(3b) is methyl.

Embodiment 40

-   -   A compound of Formula 1 or any one of Embodiments 1 through 39        wherein R⁴ is halogen or —SC≡N.

Embodiment 41

-   -   A compound of Embodiment 40 wherein R⁴ is —SC≡N.

Embodiment 42

-   -   A compound of Embodiment 40 wherein R⁴ is halogen.

Embodiment 43

-   -   A compound of Embodiment 42 wherein R⁴ is Br, Cl or F.

Embodiment 44

-   -   A compound of Formula 1 or any one of Embodiments 1 through 39        wherein R⁴ is —OR⁷.

Embodiment 45

-   -   A compound of Formula 1 or any one of Embodiments 1 through 44        wherein R⁴ is Br, Cl, F, —OR⁷ or —SC≡N.

Embodiment 46

-   -   A compound of Embodiment 45 wherein R⁴ is Br, Cl, F or —OR⁷.

Embodiment 47

-   -   A compound of Formula 1 or any one of Embodiments 1 through 46        wherein R⁵ is H or methyl.

Embodiment 48

-   -   A compound of Embodiment 47 wherein R⁵ is H.

Embodiment 49

-   -   A compound of Formula 1 or any one of Embodiments 1 through 48        wherein R⁷ is H, C₁-C₃ alkyl, C₂-C₆ alkenyl, C₁-C₃ haloalkyl,        cyclopropyl, C₂-C₃ cyanoalkyl, C₂-C₆ alkoxyalkyl, —S(═O)₂OM¹ or        —C(═W)R⁹.

Embodiment 50

-   -   A compound of Embodiment 49 wherein R⁷ is H, C₁-C₃ alkyl, C₁-C₃        haloalkyl, cyclopropyl, C₂-C₃ cyanoalkyl, —S(═O)₂OM¹ or        —C(═W)R⁹.

Embodiment 51

-   -   A compound of Embodiment 50 wherein R⁷ is H, C₁-C₃ alkyl, C₁-C₃        haloalkyl, —S(═O)₂OM¹ or —C(═W)R⁹.

Embodiment 52

-   -   A compound of Embodiment 51 wherein R⁷ is H, methyl or —C(═W)R⁹.

Embodiment 53

-   -   A compound Embodiment 52 wherein R⁷ is H or methyl.

Embodiment 54

-   -   A compound Embodiment 53 wherein R⁷ is H.

Embodiment 55

-   -   A compound Formula 1 or any one of Embodiments 1 through 54        wherein R⁹ is methyl or methoxy.

Embodiment 56

-   -   A compound of Embodiment 55 wherein R⁹ is methyl.

Embodiment 57

-   -   A compound of Formula 1 or any one of Embodiments 1 through 56        wherein W is O.

Embodiment 58

-   -   A compound of Formula 1 or any one of Embodiments 1 through 57        wherein M¹ is Na or K.

Embodiment 59

-   -   A compound of Embodiment 58 wherein M¹ is Na.

Embodiments of this invention, including Embodiments 1-59 above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-59 above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-59 are illustrated by:

Embodiment A

A compound of Formula 1 wherein

-   -   Q¹ is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a);    -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a); or a pyrazolyl, imidazolyl,        pyridinyl, pyridazinyl, pyrazinyl or pyrimidinyl ring, each ring        optionally substituted with up to 3 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members;    -   R¹ is C₁-C₂ alkyl, —CH₂F, —CH₂Cl or cyclopropyl;    -   R² is H, halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl, halomethyl,        cyanomethyl, hydroxymethyl, C₂-C₃ alkoxyalkyl, C₁-C₂ alkoxy or        C₁-C₂ haloalkoxy;    -   each R^(3a) is independently halogen, cyano, C₁-C₂ alkyl, C₁-C₂        haloalkyl, cyclopropyl, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₂-C₃        alkylcarbonyl or —U—V-T;

each R^(3b) is independently cyano, C₁-C₂ alkyl, cyclopropyl or C₂-C₃alkoxyalkyl;

R⁴ is Br, Cl, F, —OR⁷ or —SC≡N;

R⁵ is H or methyl;

R⁷ is H, C₁-C₃ alkyl, C₂-C₆ alkenyl, C₁-C₃ haloalkyl, cyclopropyl, C₂-C₃cyanoalkyl, C₂-C₆ alkoxyalkyl, —S(═O)₂OM¹ or —C(═W)R⁹;

R⁹ is methyl or methoxy;

-   -   each U is independently O, N(R¹⁰) or a direct bond;    -   each R¹⁰ is independently H or methyl;    -   each V is independently C₁-C₃ alkylene, wherein up to 1 carbon        atom is selected from C(═O);    -   each T is independently N(R^(11a))(R^(11b)) or OR¹²;    -   each R^(11a) and R^(11b) is independently H or methyl;    -   each R¹² is independently H, C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   W is O; and    -   M¹ is Na or K.

Embodiment B

A compound of Embodiment A wherein

Q² is a phenyl ring substituted with 1 to 3 substituents independentlyselected from R^(3a); or a pyrazolyl, imidazolyl or pyridinyl ring, eachring optionally substituted with 1 to 3 substituents independentlyselected from R^(3a) on carbon atom ring members and R^(3b) on nitrogenatom ring members;

-   -   R¹ is methyl, —CH₂F or —CH₂Cl;    -   R² is halogen, cyano, C₁-C₂ alkyl, halomethyl, cyanomethyl,        hydroxymethyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy;    -   each R^(3a) is independently halogen, cyano, methyl, halomethyl,        cyclopropyl, methoxy, methylthio, methylcarbonyl or —U—V-T;    -   each R^(3b) is methyl;    -   R⁴ is Br, Cl, F or —OR⁷;    -   R⁷ is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, —S(═O)₂OM¹ or —C(═W)R⁹;    -   each U is independently O, NH or a direct bond;    -   each V is C₁-C₃ alkylene; and    -   each R¹² is independently H, methyl or halomethyl.

Embodiment C

A compound of Embodiment B wherein

-   -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a);    -   R¹ is methyl;    -   R² is halogen, cyano, methyl, halomethyl or methoxy;    -   each R^(3a) is independently halogen, cyano, methyl, halomethyl        or methoxy;

R⁴ is —OR⁷;

-   -   R⁵ is H;    -   R⁷ is H, methyl or —C(═W)R⁹; and    -   R⁹ is methyl.

Embodiment D

A compound of Embodiment C wherein

-   -   R² is Br, Cl, methyl or methoxy;    -   each R^(3a) is independently halogen, cyano or methoxy; and

R⁷ is H.

Embodiment E

A compound of Embodiment D wherein

-   -   R² methyl;    -   each R^(3a) is independently Br, Cl, F, cyano or methoxy; and    -   one of Q¹ and Q² is substituted with 2 to 3 substituents and the        other of Q¹ and Q² is substituted with 1 to 2 substituents.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of:

-   α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   (αS)-α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   (αR)-α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-5-(2,6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   (αS)-α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   (αR)-α-(2-chloro-4-fluorophenyl)-5-(2,6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   α,5-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   5-(2-bromophenyl)-α-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-5-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-1,3-dimethyl-5-(2,4,6-trifluorophenyl)-1H-pyrazole-4-methanol;-   α-(2-bromo-4-fluorophenyl)-5-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2-bromo-4-fluorophenyl)-5-(2-chloro-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   3-bromo-5-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;-   5-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   5-(2,4-dichlorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   5-(2-chloro-6-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2,4-difluorophenyl)-5-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   4-[4-[(2,4-difluorophenyl)hydroxymethyl]-1,3-dimethyl-1H-pyrazol-5-yl]-3,5-difluorobenzonitrile;-   5-(2-chloro-6-fluorophenyl)-α-(2,4-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   5-(2-chloro-6-fluorophenyl)-α-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-α-(2,4,6-trifluorophenyl)-1H-pyrazole-4-methanol;-   5-(2-bromo-4-fluorophenyl)-1,3-dimethyl-α-(2,4,6-trifluorophenyl)-1H-pyrazole-4-methanol;-   5-(2-chloro-6-fluorophenyl)-α-(2-chloro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;-   3-bromo-α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;-   3-chloro-α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;-   5-(2,6-difluorophenyl)-α-(4-fluoro-2-methylphenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-methoxphenyl)-5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;-   5-(2,6-difluorophenyl)-3-methoxy-α-(4-methoxy-2-methylphenyl)-1-methyl-1H-pyrazole-4-methanol;-   5-(2-chloro-6-fluorophenyl)-α-(2-chloro-4-methoxyphenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;-   3-chloro-5-(2,6-difluorophenyl)-α-(4-methoxy-2-methylphenyl)-1-methyl-1H-pyrazole-4-methanol;-   3-chloro-5-(2,6-difluorophenyl)-α-(2-fluoro-4-methoxyphenyl)-1-methyl-1H-pyrazole-4-methanol;-   3-chloro-α-(2-chloro-4-methoxyphenyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;    and-   3-bromo-5-(2,6-difluorophenyl)-α-(4-methoxy-2-methylphenyl)-1-methyl-1H-pyrazole-4-methanol.

As noted in the Summary of the Invention, this invention is alsodirected to a compound of Formula 1A. Embodiments of Formula 1A includethose described in the Summary of the Invention as well as theEmbodiments below. In the following Embodiments, Formula 1A includesstereoisomers, N-oxides and salts thereof, and reference to “a compoundof Formula 1A” includes the definitions of substituents specified in theSummary of the Invention unless further defined in the Embodiments.

Embodiment A1

-   -   A compound of Formula 1A wherein Q¹ is a phenyl ring substituted        with 1 to 3 substituents independently selected from R^(3a).

Embodiment A2

-   -   A compound of Embodiment A1 wherein Q¹ is a phenyl ring        substituted with 2 to 3 substituents independently selected from        R^(3a).

Embodiment A3

-   -   A compound of Embodiment A1 wherein Q¹ is a phenyl ring        substituted with 1 substituent independently selected from        R^(3a).

Embodiment A4

-   -   A compound of Embodiment A1 wherein Q¹ is a phenyl ring        substituted with 2 substituents independently selected from        R^(3a).

Embodiment A5

-   -   A compound of Embodiment A1 wherein Q¹ is a phenyl ring        substituted with 3 substituents selected from R^(3a).

Embodiment A6

-   -   A compound of Formula 1A or any one of Embodiments A1 through A5        wherein Q¹ is a phenyl ring substituted with at least one R^(3a)        substituent attached at an ortho position (relative to the        connection of the Q¹ ring to the remainder of Formula 1A).

Embodiment A7

-   -   A compound of Formula 1A or any one of Embodiments A1 through A6        wherein Q¹ is a phenyl ring substituted with two R^(3a)        substituents attached at an ortho position and the para position        (relative to the connection of the Q¹ ring to the remainder of        Formula 1A).

Embodiment A8

-   -   A compound of Formula 1A or any one of Embodiments A1 through A6        wherein Q¹ is a phenyl ring substituted with two R^(3a)        substituents attached at both ortho positions (relative to the        connection of the Q¹ ring to the remainder of Formula 1A).

Embodiment A9

-   -   A compound of Formula 1A or any one of Embodiments A1 through A6        wherein Q¹ is a phenyl ring substituted with three R^(3a)        substituents attached at both ortho positions and the para        position (relative to the connection of the Q¹ ring to the        remainder of Formula 1A).

Embodiment A10

-   -   A compound of Formula 1A or any one of Embodiments A1 through A9        wherein Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a); or a pyrazolyl, imidazolyl,        pyridinyl, pyridazinyl, pyrazinyl or pyrimidinyl ring, each ring        optionally substituted with up to 3 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members.

Embodiment A11

-   -   A compound of Embodiment A10 wherein Q² is a phenyl ring        substituted with 1 to 3 substituents independently selected from        R^(3a); or a pyrazolyl, imidazolyl or pyridinyl ring, each ring        optionally substituted with 1 to 3 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members.

Embodiment A12

-   -   A compound of Embodiment A11 wherein Q2 is a phenyl ring        substituted with 1 to 3 substituents independently selected from        R^(3a).

Embodiment A13

-   -   A compound of Embodiment A12 wherein Q² is a phenyl ring        substituted with 2 to 3 substituents independently selected from        R^(3a).

Embodiment A14

-   -   A compound of Embodiment A13 wherein Q² is a phenyl ring        substituted with 1 substituent independently selected from        R^(3a).

Embodiment A15

-   -   A compound of Embodiment A13 wherein Q² is a phenyl ring        substituted with 2 substituents independently selected from        R^(3a).

Embodiment A16

-   -   A compound of Embodiment A13 wherein Q² is a phenyl ring        substituted with 3 substituents independently selected from        R^(3a).

Embodiment A17

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A16 wherein Q² is a phenyl ring substituted with two R^(3a)        substituents attached at an ortho position and the para position        (relative to the connection of the Q² ring to the remainder of        Formula 1A).

Embodiment A18

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A17 wherein Q² is a phenyl ring substituted with two R^(3a)        substituents attached at both ortho positions (relative to the        connection of the Q² ring to the remainder of Formula 1A).

Embodiment A19

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A18 wherein Q² is a phenyl ring substituted with three R^(3a)        substituents attached at both ortho positions and the para        position (relative to the connection of the Q² ring to the        remainder of Formula 1A).

Embodiment A20

-   -   A compound of Embodiment A11 wherein Q² is a pyridinyl ring        optionally substituted with up to 3 substituents independently        selected from R^(3a).

Embodiment A21

-   -   A compound of Embodiment A20 wherein Q² is a pyridinyl ring        substituted with 1 to 3 substituents independently selected from        R^(3a).

Embodiment A22

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A21 wherein when Q² is a 6-membered fully unsaturated        heterocyclic ring (e.g., pyridinyl, pyridazinyl, pyrazinyl or        pyrimidinyl), then Q² is substituted with at least one R^(3a)        substituent attached at an ortho position (relative to the        connection of the Q² ring to the remainder of Formula 1A).

Embodiment A23

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A22 wherein when Q¹ and Q² are each a phenyl ring substituted        with 1 to 3 substituents independently selected from R^(3a),        then one ring substituted with 2 to 3 substituents and the other        ring substituted with 1 to 3 substituents.

Embodiment A24

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A23 wherein when Q¹ and Q² are each a phenyl ring substituted        with 1 to 3 substituents independently selected from R^(3a),        then one ring is substituted with 2 to 3 substituents and the        other ring is substituted with 1 to 2 substituents.

Embodiment A25

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A24 wherein when Q¹ and Q² are each a phenyl ring substituted        with 1 to 3 substituents independently selected from R^(3a),        then one ring is substituted with 3 substituents and the other        ring is substituted with 2 substituents.

Embodiment A26

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A25 wherein Q¹ and Q² are both a phenyl ring substituted with 2        substituents independently selected from R^(3a).

Embodiment A27

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A26 wherein X is O, S, N(R⁶) or C(═O).

Embodiment A28

-   -   A compound of Embodiment A27 wherein X is O, NH or C(═O).

Embodiment A29

-   -   A compound of Embodiment A27 wherein X is N(R⁶).

Embodiment A29a

-   -   A compound of Embodiment A29 wherein X is NH.

Embodiment A30

-   -   A compound of Embodiments A28 wherein X is O.

Embodiment A31

-   -   A compound of Embodiment A28 wherein X is C(═O).

Embodiment A32

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A31 wherein R¹ is C₁-C₂ alkyl, —CH₂F, —CH₂Cl or cyclopropyl.

Embodiment A33

-   -   A compound of Embodiment A32 wherein R¹ is methyl, —CH₂F or        —CH₂Cl.

Embodiment A34

-   -   A compound of Embodiment A33 wherein R¹ is methyl.

Embodiment A35

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A34 wherein R² is H, halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl,        halomethyl, cyanomethyl, hydroxymethyl, C₂-C₃ alkoxyalkyl, C₁-C₂        alkoxy or C₁-C₂ haloalkoxy.

Embodiment A36

-   -   A compound of Embodiment A35 wherein R² is halogen, cyano, C₁-C₂        alkyl, halomethyl, cyanomethyl, hydroxymethyl, C₁-C₂ alkoxy or        C₁-C₂ haloalkoxy.

Embodiment A37

-   -   A compound of Embodiment A36 wherein R² is halogen, cyano, C₁-C₂        alkyl, halomethyl, cyanomethyl, hydroxymethyl or methoxy.

Embodiment A38

-   -   A compound of Embodiment A37 wherein R² is halogen, cyano,        methyl, halomethyl or methoxy.

Embodiment A39

-   -   A compound of Embodiment A38 wherein R² is Br, Cl, F, cyano,        methyl or methoxy.

Embodiment A40

-   -   A compound of Embodiment A39 wherein R² is Br, Cl, methyl or        methoxy.

Embodiment A41

-   -   A compound of Embodiment A40 wherein R² is methyl.

Embodiment A42

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A41 wherein each R^(3a) is independently halogen, cyano, C₁-C₂        alkyl, C₁-C₂ haloalkyl, cyclopropyl, C₁-C₂ alkoxy, C₁-C₂        alkylthio, C₂-C₃ alkylcarbonyl or —U—V-T.

Embodiment A43

-   -   A compound of Embodiment A42 wherein each R^(3a) is        independently halogen, cyano, methyl, halomethyl, cyclopropyl,        methoxy, methylthio, methylcarbonyl or —U—V-T.

Embodiment A44

-   -   A compound of Embodiment A43 wherein each R^(3a) is        independently halogen, cyano, methyl, halomethyl or methoxy.

Embodiment A45

-   -   A compound of Embodiment A44 wherein each R^(3a) is        independently halogen, cyano or methoxy.

Embodiment A46

-   -   A compound of Embodiment A45 wherein each R^(3a) is        independently Br, Cl, F, cyano or methoxy.

Embodiment A47

-   -   A compound of Embodiment A46 wherein each R^(3a) is        independently Cl or F.

Embodiment A48

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A47 wherein each U is independently O, N(R¹⁰) or a direct bond.

Embodiment A49

-   -   A compound of Embodiment A48 wherein each R¹⁰ is independently H        or methyl.

Embodiment A50

-   -   A compound of Embodiment A48 wherein each U is independently O,        NH or a direct bond.

Embodiment A51

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A50 wherein each V is independently C₁-C₄ alkylene, wherein up        to 1 carbon atom is selected from C(═O).

Embodiment A52

-   -   A compound of Embodiment A51 wherein each V is independently        C₁-C₃ alkylene.

Embodiment A53

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A52 wherein each T is independently N(R^(11a))(R^(11b)) or OR¹².

Embodiment A54

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A53 wherein each R^(11a) and R^(11b) is independently H, C₁-C₆        alkyl or C₁-C₆ haloalkyl.

Embodiment A55

-   -   A compound of Embodiment A54 wherein each R^(11a) and R^(11b) is        independently H or methyl.

Embodiment A56

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A55 wherein each R¹² is independently H, C₁-C₆ alkyl or C₁-C₆        haloalkyl.

Embodiment A57

-   -   A compound Embodiment A56 wherein each R¹² is independently H,        methyl or halomethyl.

Embodiment A58

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A57 wherein each R^(3b) is independently cyano, C₁-C₂ alkyl,        cyclopropyl or C₂-C₃ alkoxyalkyl.

Embodiment A59

-   -   A compound of Embodiment A58 wherein each R^(3b) is methyl.

Embodiment A60

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A59 wherein R⁶ is H, hydroxy, C₁-C₃ alkyl, C₁-C₃ haloalkyl,        C₂-C₃ alkoxyalkyl, —CH(═O), —OR⁷, —OS(═O)₂M¹, —S(═O)_(n)R⁸ or        —C(═W)R⁹.

Embodiment A61

-   -   A compound of Embodiments A60 wherein R⁶ is H, methyl,        halomethyl or —OR⁷.

Embodiment A62

-   -   A compound of Embodiment A61 wherein R⁶ is H.

Embodiment A63

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A62 wherein R⁷ is H, C₁-C₃ alkyl, C₂-C₆ alkenyl, C₁-C₃        haloalkyl, cyclopropyl, C₂-C₃ cyanoalkyl, C₂-C₆ alkoxyalkyl,        —S(═O)₂OM¹ or —C(═W)R⁹.

Embodiment A64

-   -   A compound of Embodiment A63 wherein R⁷ is H, C₁-C₃ alkyl, C₁-C₃        haloalkyl, cyclopropyl, C₂-C₃ cyanoalkyl, —S(═O)₂OM¹ or        —C(═W)R⁹.

Embodiment A65

-   -   A compound of Embodiment A64 wherein R⁷ is H, C₁-C₃ alkyl, C₁-C₃        haloalkyl, —S(═O)₂OM¹ or —C(═W)R⁹.

Embodiment A66

-   -   A compound of Embodiment A65 wherein R⁷ is H, methyl or        —C(═W)R⁹.

Embodiment A67

-   -   A compound Embodiment A66 wherein R⁷ is H or methyl.

Embodiment A68

-   -   A compound Embodiment A67 wherein R⁷ is H.

Embodiment A69

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A68 wherein R⁸ is methyl.

Embodiment A70

-   -   A compound Formula 1A or any one of Embodiments A1 through A69        wherein R⁹ is methyl or methoxy.

Embodiment A71

-   -   A compound of Embodiment A70 wherein R⁹ is methyl.

Embodiment A72

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A72 wherein W is O.

Embodiment A73

-   -   A compound of Formula 1A or any one of Embodiments A1 through        A72 wherein M¹ is Na or K.

Embodiment A74

-   -   A compound of Embodiment A73 wherein M¹ is Na.

Embodiments of this invention, including Embodiments A1-A74 above aswell as any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1A but also to the starting compoundsand intermediate compounds useful for preparing the compounds of Formula1A. In addition, embodiments of this invention, including EmbodimentsA1-A74 above as well as any other embodiments described herein, and anycombination thereof, pertain to the compositions and methods of thepresent invention.

Combinations of Embodiments A1-A74 are illustrated by:

Embodiment F

A compound of Formula 1A wherein

-   -   Q¹ is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a);    -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a); or a pyrazolyl, imidazolyl,        pyridinyl, pyridazinyl, pyrazinyl or pyrimidinyl ring, each ring        optionally substituted with up to 3 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members;    -   X is O, S, N(R⁶) or C(═O);    -   R¹ is C₁-C₂ alkyl, —CH₂F, —CH₂Cl or cyclopropyl;    -   R² is H, halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl, halomethyl,        cyanomethyl, hydroxymethyl, C₂-C₃ alkoxyalkyl, C₁-C₂ alkoxy or        C₁-C₂ haloalkoxy;    -   each R^(3a) is independently halogen, cyano, C₁-C₂ alkyl, C₁-C₂        haloalkyl, cyclopropyl, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₂-C₃        alkylcarbonyl or —U—V-T;    -   each R^(3b) is independently cyano, C₁-C₂ alkyl, cyclopropyl or        C₂-C₃ alkoxyalkyl;    -   R⁶ is H, hydroxy, —CH(═O), C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₃        alkoxyalkyl, —OR⁷, —S(═O)₂OM¹, —S(═O)_(n)R⁸ or —C(═W)R⁹;    -   R⁷ is H, C₁-C₃ alkyl, C₂-C₆ alkenyl, C₁-C₃ haloalkyl,        cyclopropyl, C₂-C₃ cyanoalkyl, C₂-C₆ alkoxyalkyl, —S(═O)₂OM¹ or        —C(═W)R⁹;    -   R⁸ is methyl;    -   R⁹ is methyl or methoxy;    -   each U is independently O, N(R¹⁰) or a direct bond;    -   each R¹⁰ is independently H or methyl;    -   each V is independently C₁-C₃ alkylene, wherein up to 1 carbon        atom is selected from C(═O);    -   each T is independently N(R^(11a))(R^(11b)) or OR¹²;    -   each R^(11a) and R^(11b) is independently H or methyl;    -   each R¹² is independently H, C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   W is O; and    -   M¹ is Na or K.

Embodiment G

A compound of Embodiment F wherein

-   -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a); or a pyrazolyl, imidazolyl        or pyridinyl ring, each ring optionally substituted with 1 to 3        substituents independently selected from R^(3a) on carbon atom        ring members and R^(3b) on nitrogen atom ring members;    -   R¹ is methyl, —CH₂F or —CH₂Cl;    -   R² is halogen, cyano, C₁-C₂ alkyl, halomethyl, cyanomethyl,        hydroxymethyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy;    -   each R^(3a) is independently halogen, cyano, methyl, halomethyl,        cyclopropyl, methoxy, methylthio, methylcarbonyl or —U—V-T;    -   each R^(3b) is methyl;    -   R⁶ is H, methyl, halomethyl or —OR⁷;    -   R⁷ is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, —S(═O)₂OM¹ or —C(═W)R⁹;    -   each U is independently O, NH or a direct bond;    -   each V is C₁-C₃ alkylene; and    -   each R¹² is independently H, methyl or halomethyl.

Embodiment H

A compound of Embodiment G wherein

-   -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a);    -   R¹ is methyl;    -   R² is halogen, cyano, methyl, halomethyl or methoxy;    -   each R^(3a) is independently halogen, cyano, methyl, halomethyl        or methoxy;    -   R⁷ is H, methyl, or —C(═W)R⁹; and    -   R⁹ is methyl.

Embodiment I

A compound of Embodiment H wherein

-   -   X is O, S, NH or C(═O);    -   R² is Br, Cl, methyl or methoxy; and    -   each R^(3a) is independently halogen, cyano or methoxy.

Embodiment J

A compound of Embodiment I wherein

-   -   R² methyl;    -   each R^(3a) is independently Br, Cl, F, cyano or methoxy; and    -   one of Q¹ and Q² is substituted with 2 to 3 substituents and the        other of Q¹ and Q² is substituted with 1 to 2 substituents.

Specific embodiments include compounds of Formula 1A selected from thegroup consisting of:

-   5-(2-chloro-4-methoxyphenyl)-4-(2,4-difluorophenoxy)-1,3-dimethyl-1H-pyrazole;-   4-(2-chloro-4-fluorophenoxy)-5-(2-chloro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole;-   3-chloro-4-[4-(2-chloro-4-fluorophenoxy)-1,3-dimethyl-1H-pyrazol-5-yl]benzonitrile;-   4-[[5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]amino]-3,5-difluorobenzonitrile;-   N,5-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine;-   3-chloro-4-[[5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]oxy]benzonitrile;-   5-(2-chloro-4-fluorophenyl)-N-(2,4-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-amine;-   5-(2-chloro-4-fluorophenyl)-N-(4-chloro-2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-amine;-   4-(2-chloro-4-fluorobenzoyl)-5-(2,4-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile;-   N-(2-bromo-4-fluorophenyl)-5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-amine;-   N-(2,4-dichlorophenyl)-5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine;    and-   [5-(2,4-dichlorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl](2,4-difluorophenyl)methanone.

Of note are compounds of Formula 1 and Formula 1A (including allstereoisomers), N-oxides, and salts thereof (including but not limitedto Embodiments 1-59 and A1-A74 above) wherein R² is halogen, cyano,C₁-C₂ alkyl, halomethyl, cyanomethyl, hydroxymethyl, cyclopropyl,halocyclopropyl, methylthio or methoxy.

Of further note are compounds of Formula 1 and Formula 1A (including allstereoisomers), N-oxides, and salts thereof (including but not limitedto Embodiments 1-59 and A1-A74 above) wherein R⁷ is H, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆cyanoalkyl, —CH(═O), —S(═O)₂OM¹ or —C(═W)R⁹.

Additionally, of note are compounds of Formula 1 and Formula 1A(including all stereoisomers), N-oxides, and salts thereof (includingbut not limited to Embodiments 1-59 and A1-A74 above) wherein when eachQ¹ and Q² is a phenyl ring substituted with 1 to 5 substituentsindependently selected from R^(3a), then Q² is substituted with at leastone R^(3a) substituent at an ortho position.

Also of note are compounds of Formula 1 (including all stereoisomers),N-oxides, and salts thereof (including but not limited to Embodiments1-59 above) wherein R⁴ is halogen, —OR⁷

This invention provides a fungicidal composition comprising a compoundof Formula 1 or Formula 1A (including all stereoisomers, N-oxides, andsalts thereof), and at least one other fungicide. Of note as embodimentsof such compositions are compositions comprising a compoundcorresponding to any of the compound embodiments described above.

This invention provides a fungicidal composition comprising a compoundof Formula 1 or Formula 1A (including all stereoisomers, N-oxides, andsalts thereof) (i.e. in a fungicidally effective amount), and at leastone additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents. Of note as embodimentsof such compositions are compositions comprising a compoundcorresponding to any of the compound embodiments described above.

This invention provides a method for controlling plant diseases causedby fungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of Formula 1 or Formula 1A (including all stereoisomers,N-oxides, and salts thereof). Of note as embodiments of such methods aremethods comprising applying a fungicidally effective amount of acompound corresponding to any of the compound embodiments describeabove. Of particular note are embodiments where the compounds areapplied as compositions of this invention.

One or more of the following methods and variations as described inSchemes 1-9 can be used to prepare the compounds of Formula 1 andcompounds of Formula 1A. The definitions of Q¹, Q², R¹, R², R⁴, R⁵ and Xin the compounds of Formulae 1-17 below are as defined above in theSummary of the Invention unless otherwise noted.

Certain compounds of Formula 1 and Formula 1A can be prepared as shownin Scheme 1. In this method a compound of Formula 2 is first treatedwith an organometallic agent of Formula 3 such an alkyl lithium base(e.g., n-butyllithium, s-butyllithium or lithium diisopropylamide) or aGrignard reagent in a solvent such as toluene, ethyl ether,tetrahydrofuran or dimethoxymethane at temperatures ranging from about−78° C. to ambient temperature. Anions of Formula 2a (i.e. metallatedintermediates of Formula 2 generated in situ) are then contacted with anelectrophile of Formulae 4 or 5. The use and choice of an appropriateelectrophile of Formulae 4 or 5 will depend on the compound of Formula 1or Formula 1A desired and will be apparent to one skilled in chemicalsynthesis. For example, aldehydes of the formula Q¹CHO provide compoundsFormula 1 wherein R⁴ is OH and R⁵ is H; benzoyl chlorides of formulaQ¹C(═O)Cl or benzamides of formula Q¹C(═O)N(Me)OMe provide compoundsFormula 1A wherein X is C(═O), chlorosulfides of formula Q¹SCl ordisulfies formula of Q¹S—S-Q¹ provide compounds Formula 1A wherein X isS, and nitrosobenzenes of formula Q¹N(═O) provide compounds Formula 1Awherein X is N(OH). In cases where the electrophile is Q¹C(═O)Cl, theaddition of a second organometallic agent such as zinc chloride, zincbromide or a monovalent copper salt such as copper(I) iodide orcopper(I) cyanide before the addition of the electrophile promotesreactivity. There are a wide-variety of general methods described in thesynthetic literature for metallationialkylation reactions which can bereadily adapted to prepare compounds of the present invention. In thepresent disclosure, Example 4, Step D, Example 6 and Example 9, Step Eillustrate the method of Scheme 1.

Electrophiles of Formulae 4 and 5 are commercially available and can beprepared by methods known in the art. Compounds of Formula 2 are knownand can be prepared by the method disclosed in Scheme 3 below, and by avariety of methods disclosed in the chemical literature.

As shown in Scheme 2, compounds of Formula 1a (i.e. Formula 1 wherein R⁴is OH and R⁵ is H) can be reduced to provide the keto compounds ofFormula 1Aa (i.e. Formula 1A wherein X is C(═O)) using standardreduction techniques. Typical reaction conditions involve contacting aboron-based reducing agent such as sodium borohydride or sodiumtriacetoxyborohydride with the compound of Formula 1Aa in a solvent suchas lower alcohols or tetrahydrofuran. Other techniques known to thoseskilled in the art may also be employed. For relevant references see,for example, Organic Letters 2009, 11, 1659-1662, Journal of theAmerican Chemical Society 2006, 128, 9998-9999, and Acta ChemicaScandinavica 1991, 45, 925-929. Also, Examples 8 and 11 illustrate thepreparation of a compound of Formula 1a from the corresponding ketone ofFormula 1Aa.

As shown in Scheme 3, keto compounds of Formula 1Aa (i.e. Formula 1Awherein X is C(═O)) can also be treated with alkylmagnesium halides toprovide compounds of Formula 1b (i.e. Formula 1 wherein R⁴ is OH and R⁵is C₁-C₄ alkyl). Typically the reaction use run in presence of zincchloride and in a solvent such as diethyl ether or tetrahydrofuran attemperatures from about 0-100° C. (for references see, for example,Organic Lett. 2009, 11, 1659-1662, J. Am. Chem. Soc. 2006, 128,9998-9999, and Acta Chemica Scandinavica 1991, 45, 925-929).

In an alternate approach to the method of Scheme 1, pyrazoles of Formula1Aa (i.e. Formula 1A wherein X is C(═O)) can be prepared from compoundsof Formula 6 using Friedel-Crafts acylation conditions as illustrated inScheme 4. In this method, the compound of Formula 6 is contacted with anacid chloride of Formula 7 in the presence of a Lewis acid (e.g.,aluminum chloride, boron trifluoride diethyl etherate or tintetrachloride) in a solvent such as dichloromethane, tetrachloroethane,or nitrobenzene, at temperatures ranging between about 0 to 200° C.Present Example 7 and Example 10, Step C illustrate the method of Scheme4.

As shown in Scheme 5, Compounds of Formula 1c (i.e. Formula 1 wherein R⁴is OH) can be converted to the compounds of Formula 1d (i.e. Formula 1wherein R⁴ is halogen) using a variety of conditions published in thechemical literature. For example, treatment of a compound of Formula 1cwith a fluorinating agent (e.g., bis(2-methoxyethyl)aminosulfur(Deoxo-Fluor®), diethylaminosulfur trifluoride (DAST), HF-pyridine(Olah's reagent) or sulfur tetrafluoride) provides compounds of FormulaFormula 1d wherein R⁴ is F. For reaction conditions see C. J. Wang,Organic Reactions 2005, Vol. 34 (Wiley, New York, 1951) Chapter 2, pp.319-321; also, present Example 5 illustrates the preparation of acompound of Formula 1d wherein R⁴ is F and R⁵ is H. Compounds of Formula1d wherein R⁴ is Br can be prepared by treating the correspondingcompound of Formula 1c with hydrobromic acid in a solvent such asglacial acetic acid using the method described by Beukers et al.,Journal of Medicinal Chemistry 2004, 47(15), 3707-3709. Compounds ofFormula 1d wherein R⁴ is Cl can be prepared by treating thecorresponding compound of Formula 1c with thionyl chloride or phosphoruspentachloride in presence of a base such as triethylamine or pyridine ina solvent such as dichloromethane or pyridine at 25-110° C. Compounds ofFormula 1d wherein R⁴ is I can be prepared by reacting correspondingcompounds of Formula 1c with sodium iodide or potassium iodide inpresence of BF₃.Et₂O and an ether solvent such as 1,4-dioxane or withhydroiodic acid in a solvent such as acetonitrile at 25-70° C. accordingto general methods described in Tetrahedron Letters 2001, 42, 951-953and Journal of the American Chemical Society 1965, 87, 539-42.

As shown in Scheme 6, pyrazole intermediates of Formula 2 are readilyprepared from corresponding pyrazoles of Formula 6 by treatment with ahalogenating agent. Suitable halogenating agents for this method includeN-bromosuccinimide (NBS), N-iodosuccinimide (NIS), bromine, sodiumbromite, thionyl chloride, oxalyl chloride, phenylphosphonic dichlorideor phosgene. Particularly useful is N-bromosuccinimide (NBS) andN-iodo-succinimide (NIS). Suitable solvents for this reaction include,for example, N,N-dimethyl-formamide, N,N-dimethylacetamide,dichloromethane, chloroform, chlorobutane, benzene, xylenes,chlorobenzene, tetrahydrofuran, p-dioxane, acetonitrile, and the like.Optionally, an organic base such as triethylamine, pyridine,N,N-dimethylaniline, and the like can be added. Typical reactiontemperatures range from about ambient temperature to 200° C. Forrepresentative procedures see Czarnocki et al., Synthesis 2006, 17,2855-2864; Brana et al., Journal of Medicinal Chemistry 2005, 48,6843-6854; Liu et al., Journal of Medicinal Chemistry 2007, 50,3086-3100 and Chan et al., Journal of Medicinal Chemistry 2005, 48,4420-4431. The method of Scheme 6 is also illustrated in Example 4, StepC, Example 3, Step C and Example 9, Step D.

As shown in Scheme 7, compounds of Formula 6 can be prepared by reactionof a 4-bromo or 4-iodo pyrazole of Formula 8 undertransition-metal-catalyzed cross-coupling reaction conditions. In thismethod reaction of a pyrazole of Formula 8 with a compound of formulaQ²-M¹ in the presence of a suitable palladium, copper or nickelcatalyst, affords the corresponding compound of Formula 6. In thismethod compounds of formula Q²-M¹ are organoboronic acids (e.g., M¹ isB(OH)₂), organoboronic esters (e.g., M¹ is B(—OC(CH₃)₂C(CH₃)₂O—)),organotrifluoroborates (e.g., M¹ is BF₃K), organotin reagents (e.g., Mis Sn(n-Bu)₃, Sn(Me)₃), Grignard reagents (e.g., M¹ is MgBr or MgCl) ororganozinc reagents (e.g., M¹ is ZnBr or ZnCl). Suitable metal catalystsinclude, but are not limited to: palladium(II) acetate, palladium(II)chloride, tetrakis(triphenylphosphine)-palladium(0),bis(triphenylphosphine)palladium(II) dichloride,dichloro[1,1′-bis(diphenyl-phosphino)ferrocene]palladium(II),bis(triphenylphosphine)dichloronickel(II) and copper(I) salts (e.g.,copper(I) iodide, copper(I) bromide, copper(I) chloride, copper(I)cyanide or copper(I) triflate). Optimal conditions for each reactionwill depend on the catalyst used and the counterion attached to thecoupling reagent (i.e. M¹), as is understood by one skilled in the art.In some cases the addition of a ligand such as a substituted phosphineor a substituted bisphosphinoalkane promotes reactivity. Also, thepresence of a base such as an alkali carbonate, tertiary amine or alkalifluoride may be necessary for some reactions involving organoboronreagents of the formula Q²-M¹. For reviews of this type of reaction see:E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis,John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-CouplingReactions: A Practical Guide, Springer, N.Y., 2002; H. C. Brown et al.,Organic Synthesis via Boranes, Vol. 3, Aldrich Chemical Co., Milwaukee,Wis., 2002; Suzuki et al., Chemical Review 1995, 95, 2457-2483 andMolander et al., Accounts of Chemical Research 2007, 40, 275-286. Also,Example 9, Step C illustrates the synthesis of a compound of Formula 6using the method of Scheme 7.

Alternatively, as shown in Scheme 8, compounds of Formula 6 can beprepared by cyclization of enones of Formula 9 with an appropriatelysubstituted hydrazine of formula NH₂NHR¹ and subsequent oxidation ofpyrazolines of Formula 10. Useful oxidizing reagents include bromine(for conditions see, for example, Indian Journal of HeterocyclicChemistry, 2001, 11(1), 21-26), elemental sulfur, manganese dioxide,2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), chloranil (for conditionssee, for example, Russian Journal of Organic Chemistry 2006, 42(8),1113-1119) and oxygen optionally in the presence of a metal catalystsuch as cobalt acetate (for conditions see, for example, Tetrahedron2006, 62(11), 2492-2496, Chinese Chemical Letters 2008, 19(9),1013-1016). Useful solvents for this reaction includeN,N-dimethylformamide, tetrahydrofuran, toluene, water, dichloromethane,tetrachloroethane, and mixtures of these or similar solvents, attemperatures from ambient to 200° C. The reaction of hydrazines withenones and the preparation of the enones is well-known in the art (see,for example, Berichte der Deutschen Chemischen Gesellschaft [Abteilung]B: Abhandlungen 1925, 58B, 1974-86, and Journal of the American ChemicalSociety 1958, 80, 5524-7). Also, Example 4, Step B illustrates thesynthesis of a compound of Formula 6 by the method of Scheme 8.

As shown in Scheme 9, compounds of Formula 8 can be prepared byalkylation of the corresponding pyrazole of Formula 11 with analkylating agent of formula R¹-L wherein L is a leaving group such ashalogen or (halo)alkylsulfonate (e.g., Cl, Br, I, p-toluenesulfonate,methanesulfonate or trifluoromethanesulfonate). General procedures foralkylations of this type are well-known in the art and can be readilyadapted to prepare compounds of the present invention. Particularlyuseful alkylating agents for preparing compounds of Formula 8 wherein R¹is methyl are diazomethane or iodomethane using general procedures knownin the art, such as those described in Journal of Heterocyclic Chemistry1988, 1307-1310. Example 9, Step B illustrates the method of Scheme 9for the preparation of a compound of Formula 8 wherein R¹ is methyl.

Starting compounds of Formula 11 are known and can be prepared by avariety of methods disclosed in the chemical literature. For a specificexample, see Example 9, Step A.

As shown in Scheme 10, Compounds of Formula 1A can also be prepared bythe reaction of compounds of Formula 12 (e.g., 4-aminopyrazoles ofFormula 12 for X being N(R⁶), 4-hydroxypyrazoles (4-pyrazolones) ofFormula 12 for X being 0, and 4-mercaptopyrazoles of Formula 12 for Xbeing S) with compounds of Formula 13 where L is a leaving group such ashalogen or (halo)alkylsulfonate (e.g., Cl, Br, I, p-toluenesulfonate,methanesulfonate or trifluoromethanesulfonate), optionally in thepresence of a metal catalyst, and generally in the presence of a baseand a polar aprotic solvent such as N,N-dimethylformamide or dimethylsulfoxide. Compounds of Formula 13 in which Q¹ is a phenyl ringsubstituted with electron-withdrawing substituents react with Formula 12compounds by direct displacement of the leaving group L from the Q¹ ringto provide compounds of Formula 1A. Typically for these types ofreactions L is F or Cl. Compounds of Formula 13 wherein Q¹ is phenyl notsubstituted with an electron-withdrawing substituent, or in general, toimprove reaction rate, yield or product purity, the use of a metalcatalyst (e.g., metal or metal salt) in amounts ranging from catalyticup to superstoichiometric can facilitate the desired reaction. Typicallyfor these conditions, L is Br or I or a sulfonate such as —OS(O)₂CF₃ or—OS(O)₂(CF₂)₃CF₃. For example, the reaction can be run in the presenceof a metal catalyst such as copper salt complexes (e.g., CuI withN,N′-dimethylethylenediamine, proline or bipyridyl), palladium complexes(e.g., tris-(dibenzylideneacetone)dipalladium(0)) or palladium salts(e.g., palladium acetate) with ligands such as4,5-bis(diphenylphosphino)-9,9-dimethylxanthene,2-dicyclohexyl-phosphino-2′,4′,6′-triisopropylbiphenyl or2,2′-bis(diphenylphosphino)1,1′-binaphthalene, with a base such aspotassium carbonate, cesium carbonate, sodium phenoxide or sodiumtert-butoxide, in a solvent such as N,N-dimethylformamide,1,2-dimethoxyethane, dimethyl sulfoxide, 1,4-dioxane or toluene,optionally containing an alcohol such as ethanol. The method of Scheme10 is illustrated in Example 1, Step C and Example 2, Step G.

Compounds of Formula 12 are commercially available and their preparationis known in the art; see, for example, Journal für Praktische Chemie(Liepzig) 1911, 83, 171-182 and Journal of the American Chemical Society1954, 76, 501-503. Also, present Example 1, Steps A through B andExample 2, Steps A through F illustrate methods for preparing4-aminopyrazoles of Formula 12.

As illustrated in Scheme 11, compounds of Formula 1Ab (i.e. Formula 1Awherein X is NH) can also be prepared by reaction of compounds ofFormula 14 with compounds of Formula 15 under metal-catalyzed conditionssimilar to those described above for Scheme 7.

Compounds of Formula 14 are known and can be prepared by the methoddisclosed in Scheme 6, and by a variety of methods disclosed in thechemical literature.

As shown in Scheme 12, compounds of Formula 1A can also be prepared byreaction of a 5-bromo or 5-iodo pyrazole of Formula 16 with anorganometallic compound of Formula 17 under transition-metal-catalyzedcross-coupling reaction conditions analogous to those described forScheme 7. Reaction of a pyrazole of Formula 16 with a boronic acid,trialkyltin, zinc or organomagnesium reagent of Formula 16 in thepresence of a palladium or nickel catalyst and optionally a ligand(e.g., triphenylphosphine, dibenzylideneacetone,dicyclohexyl(2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphine) and a base,if needed, affords the corresponding compound of Formula 1A. Forexample, a compound of Formula 17 wherein M is B(OH)₂,B(OC(CH₃)₂C(CH₃)₂O)), B(O-i-Pr)₃Li reacts with a 5-bromo- or5-iodopyrazole of Formula 16 in the presence ofdichlorobis(triphenylphosphine) palladium(II) and aqueous base such assodium carbonate or potassium hydroxide, in solvents such as1,4-dioxane, 1,2-dimethoxyethane, toluene or ethyl alcohol, or underanhydrous conditions with the use of a ligand such as phosphine oxide orphosphite ligand (e.g., diphenylphosphine oxide) and potassium fluoridein a solvent such as 1,4-dioxane to provide the corresponding compoundof Formula 1A (for references, see Angewandte Chemie, InternationalEdition 2008, 47(25), 4695-4698 and Journal of the American ChemicalSociety 2010, 132(40), 14073-14075). The method of Scheme 12 isillustrated in Example 3, Step D.

Compounds of Formula 16 can be prepared via halogenation methodsanalogous to those described for Scheme 6, and illustrated in Example 3,Step C.

It will be recognized by one skilled in the art that various functionalgroups can be converted into others to provide different compounds ofFormula 1 or Formula 1A. For example, compounds of Formula 1 or Formula1A in which R² is methyl, ethyl or cyclopropyl can be modified byfree-radical halogenation to form compounds of Formula 1 or Formula 1Awherein R² is halomethyl or halocyclopropyl. The halomethyl compoundscan be used as intermediates to prepare compounds of Formula 1 orFormula 1A wherein R² is hydroxymethyl or cyanomethyl. Compounds ofFormula 1, Formula 1A or intermediates for their preparation may containaromatic nitro groups, which can be reduced to amino groups, and then beconverted via reactions well-known in the art, such as the Sandmeyerreaction, to various halides, providing other compounds of Formula 1 orFormula 1A. By similar known reactions, aromatic amines (anilines) canbe converted via diazonium salts to phenols, which can then be alkylatedto prepare compounds of Formula 1 or Formula 1A with alkoxysubstituents. Likewise, aromatic halides such as bromides or iodidesprepared via the Sandmeyer reaction can react with alcohols undercopper-catalyzed conditions, such as the Ullmann reaction or knownmodifications thereof, to provide compounds of Formula 1 or Formula 1Athat contain alkoxy substituents. Additionally, some halogen groups,such as fluorine or chlorine, can be displaced with alcohols under basicconditions to provide compounds of Formula 1 or Formula 1A containingthe corresponding alkoxy substituents. The resultant alkoxy compoundscan themselves be used in further reactions to prepare compounds ofFormula 1 or Formula 1A wherein R^(3a) is —U—V-T (see, for example, PCTPublication WO 2007/149448 A2). Compounds of Formula 1, Formula 1A orprecursors thereof in which R² is halide, preferably bromide or iodide,are particularly useful intermediates for transition metal-catalyzedcross-coupling reactions to prepare compounds of Formula 1 or Formula1A. These types of reactions are well documented in the literature; see,for example, Tsuji in Transition Metal Reagents and Catalysts:Innovations in Organic Synthesis, John Wiley and Sons, Chichester, 2002;Tsuji in Palladium in Organic Synthesis, Springer, 2005; and Miyaura andBuchwald in Cross Coupling Reactions: A Practical Guide, 2002; andreferences cited therein.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 or Formula 1A may not becompatible with certain functionalities present in the intermediates. Inthese instances, the incorporation of protection/deprotection sequencesor functional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1 and Formula 1A. Oneskilled in the art will also recognize that it may be necessary toperform a combination of the steps illustrated in the above schemes inan order other than that implied by the particular sequence presented toprepare the compounds of Formula 1 and or Formula 1A.

One skilled in the art will also recognize that compounds of Formula 1,Formula 1A and the intermediates described herein can be subjected tovarious electrophilic, nucleophilic, radical, organometallic, oxidation,and reduction reactions to add substituents or modify existingsubstituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Steps in the following Examples illustrate a procedure foreach step in an overall synthetic transformation, and the startingmaterial for each step may not have necessarily been prepared by aparticular preparative run whose procedure is described in otherExamples or Steps. Percentages are by weight except for chromatographicsolvent mixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. MPLC refers to medium pressure liquid chromatography onsilica gel. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; “s” means singlet, “d” means doublet, “t” meanstriplet, “m” means multiplet, “dd” means doublet of doublets, “dt” meansdoublet of triplets and “br s” means broad singlet.

Example 1 Preparation of4-[[5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]amino]-3,5-difluorobenzonitrile(Compound 40) Step A: Preparation of5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-4-nitro-1H-pyrazole

A mixture of 5-chloro-1,3-dimethyl-4-nitro-1H-pyrazole (2.50 g, 14.3mmol), 2-chloro-4-fluorophenylboronic acid (2.98 g, 17.2 mmol), cesiumcarbonate (5.58 g, 17.2 mmol) anddichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II)dichloro-methane complex (1:1) (1.16 g, 1.43 mmol) in dioxane (50 mL)was heated at 100° C. for approximately 2.5 days. After cooling to roomtemperature, the reaction mixture was filtered through a pad of Celite®(diatomaceous earth) on a sintered glass frit funnel and the filtratewas concentrated under reduced pressure. The resulting material wasdissolved in ethyl acetate and filtered through a plug of silica on asintered glass frit funnel and the filtrate was concentrated underreduced pressure. The resulting material was purified by silica gelcolumn chromatography (5 to 40% gradient of ethyl acetate in hexanes aseluant) to provide the title compound (0.32 g).

¹H NMR (CDCl₃): δ 7.32-7.26 (m, 2H), 7.16-7.09 (m, 1H), 3.58 (s, 3H),2.57 (s, 3H).

Step B: Preparation of5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine

A mixture of5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-4-nitro-1H-pyrazole (i.e. theproduct of Step A) (0.2 g, 0.74 mmol), iron powder (0.2 g, 3.6 mmol) andsaturated aqueous ammonium chloride solution (1 mL) in ethanol (5 mL)was heated at 80° C. for 4 h. After cooling to room temperature, thereaction mixture was diluted with ethyl acetate and filtered through apad of Celite® (diatomaceous earth) on a sintered glass frit funnel. Thefiltrate was concentrated under reduced pressure and the resultingmaterial was purified by silica gel column chromatography (ethyl acetateas eluant) to provide the title compound (0.14 g).

¹H NMR (CDCl₃): δ 7.36-7.20 (m, 2H), 7.17-7.05 (m, 1H), 3.57 (s, 3H),2.66 (br s, 2H), 2.24 (s, 3H).

Step C: Preparation of4-[[5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]amino]-3,5-difluorobenzonitrile

A mixture of 5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amin(i.e. the product of Step B) (0.25 g, 1.0 mmol),3,4,5-trifluorobenzonitrile (0.188 g, 1.2 mmol) and cesium carbonate(0.390 g, 1.2 mmol) in acetonitrile (3 mL) was heated at 210° C. in aBiotage Initiator™ microwave apparatus for 2 h. After cooling to roomtemperature, the reaction mixture was diluted with ethyl acetate andfiltered through a pad of silica gel on a sintered glass frit funnel.The filtrate was concentrated under reduced pressure and the resultingmaterial was purified by silica gel chromatography (30% ethyl acetate inhexanes as eluant) to provide the title compound, a compound of thepresent invention, as a solid (0.065 g).

¹H NMR (CDCl₃): δ 7.34-7.16 (m, 2H), 7.04 (m, 3H), 5.27 (br s, 1H), 3.64(s, 3H), 2.18 (s, 3H).

Example 2 Preparation of4-(4-chloro-2-fluorophenyl)-5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine(Compound 45) Step A: Preparation of methyl 3-(methylamino)-2-butenoate

To a mixture of methyl acetoacetate (23.2 g, 0.2 mol) in water (15 mL)at 10° C. was added dropwise methylamine (40% aqueous solution, 18.6 g,0.24 mol). The reaction mixture was allowed to warm to room temperatureand stirred for 2 h. The resulting solid precipitate was collected byfiltration and washed with ice water (2×), and then dried in a vacuumoven at 55° C. overnight to provide the title compound as a white solid(20.9 g).

¹H NMR (CDCl₃): δ 8.45 (br s, 1H, NH), 4.47 (s, 1H), 3.62 (s, 3H), 2.91(d, 3H), 1.92 (s, 3H).

Step B: Preparation of methyl2-chloro-4-fluoro-α-[1-(methylamino)ethylidene]-β-oxobenzenepropanoate

To a mixture of methyl 3-(methylamino)-2-butenoate (i.e. the product ofStep A) (10.25 g, 79.43 mmol) and triethylamine (13.26 mL, 9.63 g, 95.31mmol) in toluene (125 mL) at 0° C. was added dropwise2-chloro-4-fluorobenzoyl chloride (15.25 g, 79.48 mol) in toluene (25mL) over 30 minutes while maintaining the temperature of the reactionmixture between about 0 to 5° C. The reaction mixture was allowed towarm to room temperature and stirred over night. The reaction mixturewas filtered and the filtrate was concentrated under reduced pressure.The resulting dark yellow oil was triturated with hexanes and filteredto provide the title compound as a white solid (15.91 g).

¹H NMR (CDCl₃): δ 12.60 (s, 1H), 7.20-6.90 (m, 3H), 3.30 (s, 3H), 3.11(s, 3H), 2.35 (s, 3H).

Step C: Preparation of methyl5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-carboxylate

A mixture of methyl2-chloro-4-fluoro-α-[1-(methylamino)ethylidene]-β-oxobenzenepropanoate(i.e. the product of Step B) (15.91 g, 55.82 mmol) and methylhydrazine(3 mL, 56 mmol) in diethyl ether (150 mL) was stirred at roomtemperature for 48 h. The reaction mixture was concentrated underreduced pressure to provide the title compound as a colorless oil (15g).

¹H NMR (CDCl₃): δ 7.32-7.25 (m, 2H), 7.10 (dt, 1H), 3.59 (s, 3H), 2.64(s, 3H), 2.51 (s, 3H).

Step D: Preparation of5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-carboxylic acid

A mixture of methyl5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-carboxylate (i.e.the product of Step C) (12.33 g, 43.7 mol) and sodium hydroxide (1 N, 70mL) in methanol (70 mL) was heated at reflux for 2 h. The reactionmixture was cooled to about 0° C., and then the pH of the reactionmixture was adjusted to 3 by the addition of aqueous hydrochloric acidsolution (1 N). The reaction mixture was extracted with ethyl acetate(3×70 mL) and the combined extracts were washed with saturated aqueoussodium chloride solution, dried over magnesium sulfate and filtered. Thefiltrate was concentrated under reduced pressure to provide the titlecompound as a white solid (11.14 g).

¹H NMR (CDCl₃): δ 12.00 (br s, 1H), 7.70-7.45 (m, 2H), 7.35 (dt, 1H),3.48 (s, 3H), 2.37 (s, 3H).

Step E: Preparation of methylN-[5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]carbamate

A mixture of5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-carboxylic acid(i.e. the product of Step D) (10.14 g, 37.8 mmol), diphenyl phosphorylazide (8.15 mL, 10.4 g, 37.8 mmol) and triethylamine (6.32 mL, 4.59 g,45.4 mmol) in toluene (100 mL) was stirred at room temperature for 2 h.After 2 h, the reaction mixture was added dropwise to toluene (100 mL)and heated at reflux for 2 h. The reaction mixture was cooled to about70° C., methanol (30 mL) was added dropwise, and the mixture was againheated at reflux for an additional 40 minutes. The reaction mixture wasdiluted with water (100 mL), extracted with ethyl acetate (2×40 mL) andthe combined extracts were washed with saturated aqueous sodium chloridesolution, dried over magnesium sulfate and filtered. The filtrate wasconcentrated under reduced pressure to provide the title compound as alight yellow solid (9.77 g).

¹H NMR (CDCl₃): δ 7.42-7.26 (m, 2H), 7.08 (dt, 1H), 5.68 (br s, 1H, NH),3.66 (br s, 3H), 3.62 (s, 3H), 2.24 (s, 3H).

Step F: Preparation of5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine

A mixture ofN-[5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]carbamate(i.e. the product of Step E) (7.07 g, 23.8 mmol) and aqueous sodiumhydroxide (1 N, 70 mL) in methanol (70 mL) was heated at reflux for 20h. The reaction mixture was concentrated under reduced pressure, dilutedwith water and extracted with ethyl acetate (2×30 mL). The combinedorganic layers were extracted with hydrochloric acid (1 N, 2×30 mL), andthe pH of the combined aqueous extracts was adjusted to 10 with theaddition of sodium hydroxide (1 N). The aqueous mixture was extractedwith ethyl acetate (2×40 mL). The combined organic extracts were washedwith saturated aqueous sodium chloride solution, dried over magnesiumsulfate, filtered and concentrated under reduced pressure to provide thetitle compound as a viscous yellow oil (4.36 g).

¹H NMR (CDCl₃): δ 7.35-7.28 (m, 2H), 7.11 (m, 1H), 3.57 (s, 3H), 2.60(br s, 2H, NH₂), 2.23 (s, 3H).

Step G: Preparation of4-(4-chloro-2-fluorophenyl)-5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine

A mixture of 5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-4-amine(i.e. the product of Step F) (7.07 g, 23.8 mmol),4-chloro-2-fluoroiodobenzene (256 μL, 2.0 mmol), sodium tert-butoxide(0.192 g, 2.0 mmol) and[1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (0.117 g,0.16 mmol) in toluene (5 mL) was heated at 180° C. in a BiotageInitiator™ microwave apparatus for 1 h. The resulting material waspurified by flash chromatography on a silica gel (40 g), Varian BondElute SI® column (30% ethyl acetate in hexanes as eluant) to provide thetitle compound, a compound of the present invention, as a darkpurple/brown oil (164 mg).

¹H NMR (CDCl₃): δ 7.26-7.15 (m, 2H), 7.03-6.95 (m, 2H), 6.75 (dt, 1H),6.45-6.40 (m, 1H), 5.20 (s, 1H, NH), 3.67 (s, 3H), 2.13 (s, 3H).

Example 3 Preparation of4-(2-chloro-4-fluorophenoxy)-5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole(Compound 5) Step A: Preparation of1-(2-chloro-4-fluorophenoxy)-2-propanone

A mixture of 2-chloro-4-fluorophenol (3.00 g, 20.4 mmol), chloroacetone(2.12 mL, 26.6 mmol), potassium carbonate (4.24 g, 30.7 mmol) andpotassium iodide (0.20 g, catalytic) in acetone (30 mL) was heated atreflux for 4 h, cooled and filtered. The filtrate was concentrated underreduced pressure to provide the title compound as a yellow solid (4.05g).

¹H NMR (CDCl₃): δ 7.16 (dd, J=8.0, 3.0 Hz, 1H), 6.93 (m, 1H), 6.76 (m,1H), 4.53 (s, 2H), 2.34 (s, 3H).

Step B: Preparation of4-(2-chloro-4-fluorophenoxy)-1,3-dimethyl-1H-pyrazole

A mixture of 1-(2-chloro-4-fluorophenoxy)-2-propanone (i.e. the productof Step A) (1.40 g, 6.93 mmol) and N,N-dimethylformamide dimethyl acetal(1.38 mL, 10.4 mmol) was heated to 90° C. for 3 h, and then concentratedunder reduced pressure. The resulting material was diluted with ethanol(15 mL), and then methylhydrazine (0.49 mL, 9.0 mmol) and acetic acid(0.1 mL) were added. After 15 h, the reaction mixture was concentratedunder reduced pressure and the resulting material was purified by silicagel column chromatography (5 to 40% gradient of ethyl acetate in hexanesas eluant) to provide the title compound as a brown yellow oil (680 mg).

¹H NMR (CDCl₃): δ 7.16 (m, 2H), 6.78-6.88 (m, 2H), 3.81 (s, 3H), 2.10(s, 3H).

Step C: Preparation of5-bromo-4-(2-chloro-4-fluorophenoxy)-1,3-dimethyl-1H-pyrazole

To a mixture of 4-(2-chloro-4-fluorophenyoxy)-1,3-dimethyl-1H-pyrazole(i.e. the product of Step B) (680 mg, 2.82 mmol) and sodium carbonate(389 mg, 3.67 mmol) in dichloromethane (12 mL) at −40° C. was added asolution of bromine (474 mg, 2.96 mmol) in dichloromethane (1 mL). Afterthe addition was complete, the reaction mixture temperature wasmaintained at about −30 to −20° C. for 5 h. The reaction mixture wasdiluted with dichloromethane (50 mL) and washed with water (2×10 mL),aqueous sodium chloride solution, dried over sodium sulfate, filteredand concentrated under reduced pressure to provide the title compound asa yellow solid (720 mg).

¹H NMR (CDCl₃): δ 7.18 (dd, J=8.0, 3.0 Hz, 1H), 6.87 (m, 1H), 6.67 (m,1H), 3.82 (s, 3H), 2.10 (s, 3H).

Step D: Preparation of4-(2-chloro-4-fluorophenoxy)-5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole

A mixture of5-bromo-4-(2-chloro-4-fluorophenoxy)-1,3-dimethyl-1H-pyrazole (i.e. theproduct of Step C) (250 mg, 0.78 mmol) in 1,2-dimethoxyethane/water (5mL, 2:1) was sparged with a subsurface stream of argon for 30 minutes,and then 2,4-difluorophenylboronic acid (371 mg, 2.34 mmol), potassiumcarbonate (1.08 g, 7.82 mmol) and tetrakis(triphenylphosphine)palladium(90 mg, 0.078 mmol) were added. The reaction mixture was heated to 80°C. for 15 h, and then cooled and extracted with ethyl acetate. Theorganic layer was washed with water and saturated aqueous sodiumchloride solution, dried over sodium sulfate, filtered and concentratedunder reduced pressure. The resulting material was purified by silicagel column chromatography (5 to 30% gradient of ethyl acetate in hexanesas eluant) to provide the title compound, a compound of the presentinvention, as a pale yellow solid (150 mg) melting at 70-72° C.

¹H NMR (CDCl₃): δ 7.27 (m, 1H), 7.07 (dd, J=8.0, 3.0 Hz, 1H), 6.90 (m,2H), 6.79 (m, 1H), 6.69 (m, 1H), 3.71 (s, 3H), 2.12 (s, 3H).

Example 4 Preparation ofα-(2,4-difluorophenyl)-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol(Compound 14) Step A: Preparation of4-(2,6-difluorophenyl)-3-buten-2-one

To a mixture of 2,6-difluorobenzaldehyde (10.0 g, 70 mmol) in acetone(85 mL) was added sodium hydroxide (1 N solution, 106 mL). Afterstirring at room temperature for 1.5 h, the reaction mixture was dilutedwith saturated aqueous sodium chloride solution and extracted withchloroform (2×150 mL). The combined organic layers were dried overmagnesium sulfate, filtered and concentrated under reduced pressure. Theresulting material was purified by MPLC (0 to 20% gradient of ethylacetate in hexanes as eluant) to afford the title product as a solid(8.1 g).

¹H NMR (CDCl₃): δ 7.61 (d, 1H), 7.16 (m, 1H), 6.98 (m, 3H), 2.39 (s,3H).

Step B: Preparation of 5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole

To a mixture of 4-(2,6-difluorophenyl)-3-buten-2-one (i.e. the productof Step A) (8.1 g, 44.5 mmol) in ethanol (50 mL) was addedmethylhydrazine (2.1 g, 49 mmol). After 24 h, the reaction mixture wasconcentrated under reduced pressure. To the resulting oil (10.1 g) wasadded 1,1,2,2-tetrachloroethane (65 mL) and manganese oxide (41.7 g, 480mmol). The reaction mixture was heated at 140° C. for 20 minutes, andthen cooled to room temperature and filtered through a pad of Celite®(diatomaceous earth) on a sintered glass frit funnel rinsing withdichloromethane (2×20 mL). The filtrate was concentrated under reducedpressure and the resulting material was purified by MPLC (10 to 50%gradient of ethyl acetate in hexanes as eluant) to provide the titlecompound as a light yellow solid (4.02 g).

¹H NMR (CDCl₃): δ 7.38 (m, 1H), 7.01 (m, 2H), 6.17 (s, 1H), 3.71 (s,3H), 2.32 (s, 3H).

Step C: Preparation of4-bromo-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole

To a mixture of 5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole (i.e.the product of Step B) (1.53 g, 7.3 mmol) in N,N-dimethylformamide (20mL) at 0° C. was added portionwise N-bromosuccinimide (1.37 g, 7.7mmol). After the addition was complete, the reaction mixture was allowedto warm to room temperature and stirred for 1 h. The reaction mixturewas diluted with ice water (20 mL) and saturated aqueous sodiumbisulfite solution (15 mL), briefly stirred, and then partitionedbetween water (75 mL) and ethyl acetate (100 mL). The layers wereseparated and the aqueous layer was extracted with ethyl acetate (100mL). The combined organic layers were washed with saturated aqueoussodium chloride solution (100 mL), dried over magnesium sulfate,filtered and concentrated under reduced pressure. The resulting materialwas purified by MPLC (10 to 40% gradient of ethyl acetate in hexanes aseluant) to provide the title compound as a solid (1.84 g).

¹H NMR (CDCl₃): δ 7.52-7.42 (m, 1H), 7.10-7.01 (m, 2H), 3.71 (s, 3H),2.30 (s, 3H).

Step D: Preparation ofα-(2,4-difluorophenyl)-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol

To a mixture of 4-bromo-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole(i.e. the product of Step C) (500 mg, 1.7 mmol) in tetrahydrofuran (15mL) at −78° C. was added dropwise n-butyllithium (2.0 M in hexanes, 0.76mL, 1.9 mmol). The reaction mixture was stirred at −78° C. for about 20minutes, and then a solution of 2,4-difluorobenzaldehyde (153 μL, 1.4mmol) in tetrahydrofuran (1 mL) was added dropwise. After the additionwas complete, the reaction mixture was stirred at about −78° C. forabout 15 minutes, and then diluted with saturated aqueous ammoniumchloride solution (1 mL) and allowed to warm to room temperature. Theresulting mixture was poured onto a solid phase extraction tube (VarianChem Elute®, prepacked with diatomaceous earth) eluting with ethylacetate (50 mL). The ethyl acetate eluant was concentrated under reducedpressure and the resulting material was purified by MPLC (20 to 50%gradient of ethyl acetate in hexanes as eluant) to provide the titlecompound, a compound of the present invention, as a solid (560 mg).

¹H NMR (CDCl₃): δ 7.41-7.32 (m, 2H), 7.01-6.90 (m, 1H), 6.89-6.82 (m,1H), 6.68-6.56 (m, 2H), 5.82 (d, 1H), 3.60 (s, 3H), 2.26 (s, 3H), 2.08(br s, 1H).

Example 5 Preparation of5-(2,6-difluorophenyl)-4-[(2,4-difluorophenyl)fluoromethyl]-1,3-dimethyl-1H-pyrazole(Compound 68)

To a mixture ofα-(2,4-difluorophenyl)-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol(i.e. the product of Example 4) (70 mg, 0.20 mmol) in dichloromethane (2mL) at −78° C. was added bis(2-methoxyethyl)aminosulfur trifluoride(Deoxo-Fluor®) (40 μL, 0.24 mmol). The reaction mixture was stirredovernight at room temperature, and then cooled to −78° C. and saturatedaqueous sodium bicarbonate solution (3 mL) was added dropwise. Theresulting mixture was extracted with dichloromethane (3×) and thecombined organic layers were dried over magnesium sulfate, filtered andconcentrated under reduced pressure. The resulting material was purifiedby MPLC (50% ethyl acetate in hexanes as eluant) to provide the titlecompound, a compound of the present invention, as a solid (30 mg)

¹H NMR (CDCl₃): δ 7.40-7.31 (m, 1H), 7.28-7.20 (m, 1H), 6.98-6.82 (m,2H), 6.70-6.62 (m, 2H), 6.52 (d, 1H), 3.61 (s, 3H), 2.20 (s, 3H).

Example 6 Preparation of4-[(4-chlorophenyl)thio]-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole(Compound 56)

To a mixture of 4-bromo-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole(i.e. the product of Step C, Example 4) (250 mg, 0.87 mmol) intetrahydrofuran at −78° C. was added dropwise n-butyllithium (2.5 M inhexanes, 0.38 ml, 0.96 mmol). The reaction mixture was stirred at about−78 to 0° C. for 15 minutes, and then 4,4′-dichlorodiphenyl disulfide(0.25 g, 0.87 mmol) in tetrahydrofuran (1 mL) was added. After about 10minutes, the reaction mixture was diluted with saturated aqueousammonium chloride solution and allowed to warm to room temperature. Theresulting mixture was poured onto a solid phase extraction tube (VarianChem Elute®, prepacked with diatomaceous earth) eluting with ethylacetate. The ethyl acetate eluant was concentrated under reducedpressure and the resulting material was purified by MPLC (10 to 50%gradient of ethyl acetate in hexanes as eluant) to provide the titlecompound, a compound of the present invention, as an oil (130 mg).

¹H NMR (CDCl₃): δ 7.45-7.38 (m, 1H), 7.15-7.10 (d, 2H), 7.01-6.92 (m,2H), 6.93-6.85 (d, 2H), 3.75 (s, 3H), 2.22 (s, 3H).

Example 7 Preparation of(2,4-difluorophenyl)-[5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]methanone(Compound 32)

To a mixture of aluminum chloride (380 mg, 2.88 mmol) intetrachloroethane (10 mL) at about 0° C. was added 2,4-difluorobenzoylchloride (0.36 mL, 2.88 mmol). The reaction mixture was stirred forabout 30 minutes, and then a mixture of5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole (prepared by the methodanalogous to Example 4, Steps A-B starting with2,4-difluorobenzaldehyde) in tetrachloroethane (0.5 mL) was added. Thereaction mixture was allowed to warm to room temperature, stirred for 1h, and then heated at reflux for 24 h. The reaction mixture was cooledto room temperature, poured over a mixture of ice/hydrochloric acid andextracted with dichloromethane (3×). The combined organic layers werewashed with saturated sodium chloride solution, dried over magnesiumsulfate, filtered and concentrated under reduced pressure. The resultingmaterial was purified by MPLC (50% ethyl acetate in hexanes as eluant)to provide the title compound, a compound of the present invention, as asolid (0.16 g).

¹H NMR (CDCl₃) δ 7.28-7.38 (m, 1H), 7.08-7.01 (m, 1H), 6.79-6.70 (m,3H), 6.50-6.42 (m, 1H), 3.67 (s, 3H), 2.48 (s, 3H).

Example 8 Preparation ofα-(2,4-difluorophenyl)-5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol(Compound 72)

To a mixture of(2,4-difluorophenyl)-[5-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Example 7) (80 mg, 0.23 mmol) in ethanol (3 mL) atabout 0° C. was added sodium borohydride (38 mg, 0.92 mmol). Thereaction mixture was stirred at room temperature for 2 h, and thendiluted with ice/hydrochloric acid (about 1 mL). The resulting mixturewas poured onto a solid phase extraction tube (Varian Chem Elute®,prepacked with diatomaceous earth) eluting with ethyl acetate (75 mL).The ethyl acetate eluant was concentrated under reduced pressure and theresulting material was purified by MPLC (20 to 70% gradient of ethylacetate in hexanes as eluant) to provide the title compound, a compoundof the present invention, as a solid (63 mg).

¹H NMR (CD₃OD): δ 8.01-6.62 (m, 6H), 5.85 and 5.71 (two s, 1H) 3.54 and3.50 (two s, 3H), 2.26 and 2.13 (two s, 3H).

Example 9 Preparation of3-bromo-5-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol(Compound 30) Step A: Preparation of 3,5-dibromo-1H-pyrazole

To mixture of 3,4,5-tribromo-1H-pyrazole (10.0 g, 32.8 mmol) intetrahydrofuran (130 mL) at −70° C. under an atmosphere of argon wasadded n-butyllithium (28.8 mL, 72.1 mmol, 2.5 M in hexanes) over 20minutes. The reaction mixture was stirred at −70° C. for 2 h, and thenmethanol/tetrahydrofuran (20 mL/30 mL) was added dropwise. The reactionmixture was allowed to warm to room temperature and concentrated underreduced pressure. The resulting material was diluted with diethyl ether(500 mL), washed with aqueous hydrochloric acid (1 N, 25 mL) andsaturated aqueous sodium chloride solution (20 mL), dried over sodiumsulfate, filtered and concentrated under reduced pressure to provide thetitle compound as a yellow solid (6.20 g)

¹H NMR (DMSO-d₆): δ 6.23 (s, 1H).

Step B: Preparation of 3,5-dibromo-1-methyl-1H-pyrazole

To a mixture of sodium hydride (2.74 g 60% in mineral oil, 68.6 mmol) intetrahydrofuran (40 mL) at 0° C. was added 3,5-dibromo-1H-pyrazole (i.e.the product of Step A) (6.20 g, 27.4 mmol) in tetrahydrofuran (25 mL)over a period of 10 minutes. The reaction mixture was stirred for 1 h at0° C., and then iodomethane (3.42 mL, 54.9 mmol) was added dropwise.After 3 h the reaction mixture was allowed to warm to room temperature,saturated aqueous ammonium chloride solution (10 mL) was added and theresulting mixture was extracted with ethyl acetate (2×100 mL). Thecombined organic layers were washed with water and with saturatedaqueous sodium chloride solution, dried over sodium sulfate, filteredand concentrated under reduced pressure to provide the title compound asa brownish-yellow solid (6.0 g)

¹H NMR (CDCl₃): δ 6.29 (s, 1H), 3.85 (s, 3H).

Step C: Preparation of3-bromo-5-(2-chloro-4-fluorophenyl)-1-methyl-1H-pyrazole

A mixture of 3,5-dibromo-1-methyl-1H-pyrazole (i.e. the product of StepB) (2.00 g, 8.33 mmol) in toluene (40 mL) was sparged with a stream ofargon for 45 minutes, and then 2-chloro-4-fluorophenylboronic acid (1.59g, 9.11 mmol), potassium phosphate tribasic (5.30 g, 25.0 mmol) andtetrakis(triphenylphosphine)palladium(0) (0.48 g, 0.41 mmol) were added.The reaction mixture was heated at 90° C. for 3 h, and then cooled toroom temperature and diluted with ethyl acetate (250 mL). The mixturewas washed with water (25 mL) and saturated aqueous sodium chloridesolution, dried over sodium sulfate, filtered and concentrated underreduced pressure. The resulting material was purified by silica gelchromatography (5 to 40% gradient of ethyl acetate in hexanes as eluant)to provide the title compound as a white solid (620 mg).

¹H NMR (CDCl₃): δ 7.32-7.27 (m, 2H), 7.09 (m, 1H), 6.28 (s, 1H), 3.67(s, 3H).

Step D: Preparation of3-bromo-5-(2-chloro-4-fluorophenyl)-4-iodo-1-methyl-1H-pyrazole

To a mixture of 3-bromo-5-(2-chloro-4-fluorophenyl)-1-methyl-1H-pyrazole(i.e. the product of Step C) (620 mg, 2.14 mmol) inN,N-dimethylformamide (8 mL) at 60° C. was added N-iodosuccinimide (963mg, 4.28 mmol). The reaction mixture was stirred at 60° C. for 3 h, andthen diluted with ethyl acetate, washed with water and saturated aqueoussodium chloride solution, dried over sodium sulfate and concentratedunder reduced pressure. The material was purified by silica gelchromatography (5 to 30% gradient of ethyl acetate in hexanes as eluant)to provide the title compound as a pale yellow solid (515 mg) melting at139-141° C.

¹H NMR (CDCl₃): δ 7.30 (m, 2H), 7.15 (m, 2H), 3.72 (s, 3H).

Step E: Preparation of3-bromo-5-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol

To a mixture of3-bromo-5-(2-chloro-4-fluorophenyl)-4-iodo-1-methyl-1H-pyrazole (i.e.the product of Step D) (250 mg, 0.602 mmol) in tetrahydrofuran (3 mL) at−78° C. was added dropwise n-butyllithium (2.5 M solution in hexanes,0.36 mL, 0.90 mmol). Stirring was continued for 1 h at −78 to −40° C.,and then the reaction mixture was cooled to −78° C. and2,4-difluorobenzaldehyde (103 mg, 0.72 mmol) in tetrahydrofuran (2 mL)was added dropwise. The reaction mixture was allowed to warm to roomtemperature and stirred for 3 h, and then saturated aqueous ammoniumchloride solution was added and the mixture was extracted with ethylacetate (2×20 mL). The combined organic layers were washed with waterand saturated aqueous sodium chloride solution, dried over sodiumsulfate and concentrated under reduced pressure. The resulting materialwas purified by silica gel chromatography (10 to 50% gradient of ethylacetate in hexanes as eluant) to provide the title compound, a compoundof the present invention, as an off-white solid (35 mg).

¹H NMR (CDCl₃): δ 7.22 (m, 2H), 6.87 (m, 1H), 6.77 (m, 1H), 6.63 (m,2H), 5.90 (d, J=4.7 Hz, 1H), 3.53 (s, 3H), 2.17 (d, J=4.7 Hz, 1H).

Example 10 Preparation of4-(2-chloro-4-fluorobenzoyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile(Compound 52) Step A: Preparation of ethyl5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carboxylate

To a mixture of 2,6-difluoroacetophenone (4.7 g, 0.03 mol) and1,2-diethyl ethanedioate (4.8 g, 0.033 mol) in ethanol (33 mL) was addedsodium tert-butoxide (3.17 g, 0.033 mol). After 1 h, more ethanol (30mL) was added to the reaction mixture and stirring was continued for 1h. The reaction mixture was partitioned between hydrochloric acid (1 N)and diethyl ether. The organic phase was separated, dried over magnesiumsulfate, filtered, and concentrated under reduced pressure to half itsoriginal volume. To the resulting mixture was added methylhydrazine(1.52 g, 0.033 mol) and stirring was continued overnight. The reactionmixture was concentrated under reduced pressure and the resultingmaterial was purified by silica gel chromatography (5 to 20% gradient ofethyl acetate in methylene chloride as eluant) to provide the titlecompound as a solid (1.0 g).

¹H NMR (CDCl₃): δ 7.56-7.38 (m, 1H) 7.06 (m, 2H) 6.95 (s, 1H), 4.43 (d,2H) 3.86 (s, 3H), 1.42 (t, 3H).

Step B: Preparation of5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile

To a mixture of ammonium chloride (0.42 g, 7.52 mmol) in toluene (10 mL)at 0° C. was added dropwise trimethyl aluminum (2 M in toluene, 3.76 mL,7.52 mmol). After the addition was complete, the reaction mixture wasstirred at 0° C. for 1 h, warmed to room temperature, and then a mixtureof ethyl 5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carboxylate (i.e.the product of Step A) (1 g, 3.76 mmol) in toluene (5 mL) was added andthe mixture was heated at 110° C. for 4 h. The reaction mixture wasallowed to cool to room temperature, partitioned between aqueoushydrochloric acid (1 N) and diethyl ether (about 20 mL) and the organicphase was separated. The aqueous phase was extracted with diethyl etherand the combined organic layers were dried over magnesium sulfate,filtered and concentrated under reduced pressure. The resulting materialwas purified by silica gel column chromatography (10 to 20% gradient ofethyl acetate in hexanes) to provide the title compound as a solid (0.4g).

¹H NMR (CDCl₃): δ 7.61-7.41 (m, 1H), 7.08 (m, 2H), 6.80 (s, 1H), 3.85(s, 3H).

Step C: Preparation of4-(2-chloro-4-fluorobenzoyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile

To a mixture of aluminum chloride (0.18 g, 1.36 mmol) in1,2-dichloroethane (2 mL) was added a mixture of2-chloro-4-fluorobenzoyl chloride (0.26 g, 1.36 mmol) and5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile (i.e. theproduct of Step B) (0.15 g, 0.68 mmol) in dichloroethane (1 mL). Thereaction mixture was heated at 180° C. in a Biotage Initiator™ microwaveapparatus for 30 minutes. The resulting mixture was poured directly ontoa Varian Bond Elute SIC) column and eluted with methylene chloridefollowed by 30% ethyl acetate in hexanes to provide the title compound,a compound of the present invention, as a solid (0.07 g).

¹H NMR (CDCl₃): δ 8.12-8.03 (m, 1H), 7.41-7.57 (m, 1H), 7.40-7.33 (m,1H), 7.12-7.04 (m, 1H), 6.91-7.03 (m, 2H), 3.85 (s, 3H).

Example 11 Preparation of4-[(2-chloro-4-fluorophenyl)hydroxymethyl]-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile(Compound 53)

To a mixture of4-(2-chloro-4-fluorobenzoyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-3-carbonitrile(i.e. the product of Example 10) (0.05 g, 0.13 mmol) in ethanol (2 mL)was added sodium borohydride (0.005 g, 0.13 mmol). The reaction wasstirred for 30 minutes, and then hydrochloric acid (1 N) (0.5 mL) wasadded and the mixture was concentrated under reduced pressure. Theresulting material was diluted with methylene chloride (5 mL) and filterthrough a Celite® (diatomaceous earth) extraction tube rinsing withmethylene chloride (15 mL). The filtrate was concentrated under reducedpressure and the resulting material purified by flash chromatography ona silica gel, Varian Bond Elute SI® column (10 to 50% gradient of ethylacetate in hexanes as eluant) to provide the title compound, a compoundof the present invention, as a solid (0.03 g).

¹H NMR (CDCl₃): δ 7.63-7.54 (m, 1H), 7.53-7.40 (m, 1H), 7.06-6.91 (m,3H), 6.90-6.81 (m, 1H), 6.01 (d, 1H), 3.73 (s, 3H), 2.51 (d, 1H).

Example 12 Preparation of5-(2,6-difluorophenyl)-α-(4-fluoro-2-methylphenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol(Compound 157) Step A: Preparation of methyl3-(2,6-difluorophenyl)-2-propynoate

To a mixture of (diazomethyl)trimethylsilane (2.0 M in hexanes, 25 mL,50 mmol) in tetrahydrofuran (100 mL) at −78° C. was added n-butyllithium(2.5 M in hexanes, 20 mL, 50 mmol) over 5 minutes. After the additionwas complete, the reaction mixture temperature was maintained at about−78° C. for 30 minutes and then 2,6-difluorobenzaldehyde (7.1 g, 50mmol) was added portionwise. The reaction mixture was maintained at −78°C. for an additional 30 minutes and then allowed to warm to roomtemperature, during which time gas evolution occurred. The reactionmixture was again cooled to −78° C. and n-butyllithium (2.5 M inhexanes, 28 mL, 70 mmol) was added over 5 minutes. After 15 minutes at−78° C., methyl chloroformate (7.8 mL, 100 mmol) was added to thereaction mixture. After 30 minutes, the reaction mixture was allowed towarm to 0° C., and then partitioned between diethyl ether and saturatedammonium chloride solution. The organic phase was separated, dried overmagnesium sulfate, filtered and concentrated under reduced pressure. Theresulting material was purified by silica gel chromatography (0 to 100%gradient of ethyl acetate in hexanes as eluant) to provide the titlecompound (8.0 g).

¹H NMR (CDCl₃): δ 7.48-7.33 (m, 1H), 7.06-6.81 (m, 2H), 3.87 (s, 3H).

Step B: Preparation of5-(2,6-difluorophenyl)-1,2-dihydro-1-methyl-3H-prazol-3-one

A mixture of methyl 3-(2,6-difluorophenyl)-2-propynoate (5.0 g, 25.5mmol) (i.e. the product of Step A) and methylhydrazine (1.6 mL, 30.6mmol) in a solution of ethanol/water (25 mL, 1:1 mixture) was heated at70° C. overnight. The reaction mixture was concentrated under reducedpressure and the resulting material purified by silica gelchromatography (90% hexanes in ethyl acetate as eluant) to provide thetitle compound (2.5 g).

¹H NMR (CDCl₃): δ 11.85 (br s, 1H), 7.51-7.32 (m, 1H), 7.08-6.95 (m,2H), 5.79 (s, 1H), 3.61 (s, 3H).

Step C: Preparation of5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole

A mixture of 5-(2,6-difluorophenyl)-1,2-dihydro-1-methyl-3H-prazol-3-one(2.0 g, 9.6 mmol) (i.e. the product of Step B), potassium carbonate (1.9g, 14 mmol) and iodomethane (0.75 mL, 12 mmol) in acetonitrile (20 mL)was heated at 70° C. for 4 h and then allowed to cool to roomtemperature. After about 48 h, the reaction was diluted withdichloromethane and the resulting mixture was filtered through a pad ofCelite® (diatomaceous earth) on a sintered glass frit funnel. Thefiltrate was concentrated under reduced pressure and the resultingmaterial was purified by silica gel chromatography (0 to 100% gradientof ethyl acetate in hexanes as eluant) to provide the title compound(1.3 g).

¹H NMR (CDCl₃): δ 7.48-7.34 (m, 1H), 7.09-6.93 (m, 2H), 5.79 (s, 1H),3.92 (s, 3H), 3.62 (s, 3H).

Step D: Preparation of5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-carboxaldehyde

To a mixture of 5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole(0.5 g, 2.2 mmol) (i.e. the product of Step C) in dimethylformamide (5mL) at 80° C. was added phosphorus oxychloride (0.31 ml, 3.3 mmol).After 2 h the reaction mixture was allowed to cool to room temperature.The reaction mixture was diluted with sodium hydroxide (1 N, about 5 mL)and water. The resulting mixture was extracted with diethyl ether (2×)and the combined organic layers were washed with water, dried overmagnesium sulfate, filtered and concentrated under reduced pressure. Theresulting material was purified by silica gel chromatography (0 to 100%gradient of ethyl acetate in dichloromethane as eluant) to provide thetitle compound (0.5 g).

¹H NMR (CDCl₃): δ 9.65 (s, 1H), 7.59-7.44 (m, 1H), 7.12-7.02 (m, 2H),4.05 (s, 3H), 3.63 (s, 3H).

Step E: Preparation of5-(2,6-difluorophenyl)-α-(4-fluoro-2-methylphenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol

To a mixture of5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-carboxaldehyde(0.25 g, 0.99 mmol) (i.e. the product of Step D) in tetrahydrofuran (5mL) at −30° C. was added 4-fluoro-2-methylphenylmagnesium bromide (0.5 Min hexanes, 2.0 mL, 1.0 mmol). The reaction mixture was allowed to warmto 0° C., quenched with saturated ammonium chloride solution andconcentrated under reduced pressure. The resulting material was dilutedwith dichloromethane and water, poured onto a solid phase extractiontube (Varian Chem Elute®, prepacked with diatomaceous earth) and elutedwith dichloromethane. The dichloromethane eluant was concentrated underreduced pressure and the resulting material purified by silica gelchromatography (0 to 100% gradient of ethyl acetate in dichloromethaneas eluant) to provide the title compound (0.3 g).

¹H NMR (CDCl₃): δ 7.40-7.20 (m, 2H), 6.93-6.80 (m, 1H), 6.80-6.68 (m,1H), 6.67-6.58 (m, 1H), 6.58-6.48 (m, 1H), 5.87-5.75 (m, 1H), 4.01 (s,3H), 3.47 (s, 3H), 2.50-2.37 (m, 1H), 2.05 (s, 3H).

By the procedures described herein together with methods known in theart, the compounds disclosed in the Tables that follow can be prepared.The following abbreviations are used in the Table which follows: Memeans methyl, Et means ethyl, n-Pr means n-propyl, c-Pr meanscyclopropyl, Ph means phenyl, MeO means methoxy, EtO means ethoxy, —CNmeans cyano and —NO₂ means nitro.

TABLE 1

(R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) 2-F2-F, 4-Cl 2-Cl, 4-MeO 2,4-di-Br, 6-F 2-F, 4-MeNH(CH₂)₃O 3-F 2-Cl, 4-F2-F, 4-MeO 2-Br, 4-Cl, 6-F 2-F, 4-Me₂N(CH₂)₃O 4-F 2-F, 4-Br 2-Cl, 4-EtO2-I, 4,6-di-F 2-Cl, 4-MeO(CH₂)₃O 2-Cl 2-Cl, 4-Br 2-F, 4-EtO 4-I,2,6-di-F 2,6-di-F, 4-MeNH(CH₂)₃O 3-Cl 2-Br, 4-Cl 2,4,5-tri-F 2,6-di-Cl,4-CN 2,6-di-F, 4-MeNH(CH₂)₃ 4-Cl 2-Br, 4-F 2,3,5-tri-F 2,6-di-F, 4-CN2,6-di-F, 4-Me₂N(CH₂)₃O 2-Br 2-I, 4-F 2,3,6-tri-F 2,6-di-Cl, 4-MeO2,6-di-F, 4-MeO(CH₂)₃O 3-Br 2-Me, 4-F 2,4,6-tri-F 2,6-di-F, 4-MeO2,6-di-F, 3-MeNH(CH₂)₃O 4-Br 2-Cl, 4-CN 2,4,6-tri-Cl 2,6-di-Cl, 4-EtO2,6-di-F, 3-MeNH(CH₂)₃ 4-Me 2-F, 4-CN 2-Cl, 4,6-di-F 2,6-di-F, 4-EtO2,6-di-F, 3-Me₂N(CH₂)₃O 2,6-di-F 2-Br, 4-CN 2,6-di-Cl, 4-F 2-Br, 4-F,6-Cl 2,6-di-F, 3-MeO(CH₂)₃O 2,4-di-F 2-CF₃, 4-F 2,4-di-Cl, 6-F 2-Cl,4-Br, 6-F 2-Cl-6-F, 4-MeNH(CH₂)₃O 2,4-di-Cl 2-Me, 4-MeO 4-Cl, 2,6-di-F4-MeNH(CH₂)₃O 2-Cl-6-F, 4-MeNH(CH₂)₃ 2,6-di-Cl 2-Me, 4-EtO 2-Br,4,6-di-F 4-Me₂N(CH₂)₃O 2-Cl-6-F, 4-Me₂N(CH₂)₃O 2,4-di-Me 2-Br, 4-MeO4-Br, 2,6-di-F 4-MeO(CH₂)₃O 2-Cl-6-F, 4-MeO(CH₂)₃O Q² is 2,6-di-F—Ph andR² is Me.

The present disclosure also includes Tables 1A through 164A, each ofwhich is constructed the same as Table 1 above, except that the rowheading in Table 1 (i.e. “Q² is 2,6-di-F-Ph and R² is Me.”) is replacedwith the respective row heading shown below. For Example, in Table 1Athe row heading is “Q² is 2,6-di-F-Ph and R² is Cl”, and (R³)_(p) is asdefined in Table 1 above. Thus, the first entry in Table 1A specificallydiscloses3-chloro-5-(2,6-difluorophenyl)-N-(2-fluorophenyl)-1-methyl-1H-pyrazole-4-amine.Tables 2A through 164A are constructed similarly.

Table Row Heading  1A Q² is 2,6-di-F-Ph and R² is Cl.  2A Q² is2,6-di-F-Ph and R² is Br.  3A Q² is 2,6-di-F-Ph and R² is Et.  4A Q² is2,6-di-F-Ph and R² is CN.  5A Q² is 2,4-di-F-Ph and R² is Me.  6A Q² is2,4-di-F-Ph and R² is Cl.  7A Q² is 2,4-di-F-Ph and R² is Br.  8A Q² is2,4-di-F-Ph and R² is Et.  9A Q² is 2,4-di-F-Ph and R² is CN. 10A Q² is2,4,6-tri-F-Ph and R² is Me. 11A Q² is 2,4,6-tri-F-Ph and R² is Cl. 12AQ² is 2,4,6-tri-F-Ph and R² is Br. 13A Q² is 2,4,6-tri-F-Ph and R² isEt. 14A Q² is 2,4,6-tri-F-Ph and R² is CN. 15A Q² is 2,6-di-F-4-MeO-Phand R² is Me. 16A Q² is 2,6-di-F-4-MeO-Ph and R² is Cl. 17A Q² is2,6-di-F-4-MeO-Ph and R² is Br. 18A Q² is 2,6-di-F-4-MeO-Ph and R² isEt. 19A Q² is 2,6-di-F-4-Me-Ph and R² is CN. 20A Q² is 2,6-di-F-4-EtO-Phand R² is Me. 21A Q² is 2,6-di-F-4-EtO-Ph and R² is Cl. 22A Q² is2,6-di-F-4-EtO-Ph and R² is Br. 23A Q² is 2,6-di-F-4-EtO-Ph and R² isEt. 24A Q² is 2,6-di-F-4-EtO-Ph and R² is CN. 25A Q² is 2,6-di-F-4-CN-Phand R² is Me. 26A Q² is 2,6-di-F-4-CN-Ph and R² is Cl. 27A Q² is2,6-di-F-4-CN-Ph and R² is Br. 28A Q² is 2,6-di-F-4-CN-Ph and R² is Et.29A Q² is 2,6-di-F-4-CN-Ph and R² is CN. 30A Q² is 2-Cl-4-F-Ph and R² isMe. 31A Q² is 2-Cl-4-F-Ph and R² is Cl. 32A Q² is 2-Cl-4-F-Ph and R² isBr. 33A Q² is 2-Cl-4-F-Ph and R² is Et. 34A Q² is 2-Cl-4-F-Ph and R² isCN. 35A Q² is 2-Cl-6-F-Ph and R² is Me. 36A Q² is 2-Cl-6-F-Ph and R² isCl. 37A Q² is 2-Cl-6-F-Ph and R² is Br. 38A Q² is 2-Cl-6-F-Ph and R² isEt. 39A Q² is 2-Cl-6-F-Ph and R² is CN. 40A Q² is 2-Cl-4,6-di-F-Ph andR² is Me. 41A Q² is 2-Cl-4,6-di-F-Ph and R² is Cl. 42A Q² is2-Cl-4,6-di-F-Ph and R² is Br. 43A Q² is 2-Cl-4,6-di-F-Ph and R² is Et.44A Q² is 2-Cl-4,6-di-F-Ph and R² is CN. 45A Q² is 4-Cl-2,6-di-F-Ph andR² is Me. 46A Q² is 4-Cl-2,6-di-F-Ph and R² is Cl. 47A Q² is4-Cl-2,6-di-F-Ph and R² is Br. 48A Q² is 4-Cl-2,6-di-F-Ph and R² is Et.49A Q² is 4-Cl-2,6-di-F-Ph and R² is CN. 50A Q² is 2-Br-4-F-Ph and R² isMe. 51A Q² is 2-Br-4-F-Ph and R² is Cl. 52A Q² is 2-Br-4-F-Ph and R² isBr. 53A Q² is 2-Br-4-F-Ph and R² is Et. 54A Q² is 2-Br-4-F-Ph and R² isCN. 55A Q² is 2-Br-6-F-Ph and R² is Me. 56A Q² is 2-Br-6-F-Ph and R² isCl. 57A Q² is 2-Br-6-F-Ph and R² is Br. 58A Q² is 2-Br-6-F-Ph and R² isEt. 59A Q² is 2-Br-6-F-Ph and R² is CN. 60A Q² is 2-Me-4-F-Ph and R² isMe. 61A Q² is 2-Me-4-F-Ph and R² is Cl. 62A Q² is 2-Me-4-F-Ph and R² isBr. 63A Q² is 2-Me-4-F-Ph and R² is Et. 64A Q² is 2-Me-4-F-Ph and R² isCN. 65A Q² is 2-I-4-F-Ph and R² is Me. 66A Q² is 2-I-4-F-Ph and R² isCl. 67A Q² is 2-I-4-F-Ph and R² is Br. 68A Q² is 2-I-4-F-Ph and R² isEt. 69A Q² is 2-I-4-F-Ph and R² is CN. 70A Q² is 2-F-Ph and R² is Me.71A Q² is 2-F-Ph and R² is Cl. 72A Q² is 2-F-Ph and R² is Br. 73A Q² is2-F-Ph and R² is Et. 74A Q² is 2-F-Ph and R² is CN. 75A Q² is 2-Cl-Phand R² is Me. 76A Q² is 2-Cl-Ph and R² is Cl. 77A Q² is 2-Cl-Ph and R²is Br. 78A Q² is 2-Cl-Ph and R² is Et. 79A Q² is 2-Cl-Ph an R² is CN.80A Q² is 2-Br-Ph and R² is Me. 81A Q² is 2-Br-Ph and R² is Cl. 82A Q²is 2-Br-Ph and R² is Br. 83A Q² is 2-Br-Ph and R² is Et. 84A Q² is2-Br-Ph and R² is CN. 85A Q² is 2-F-4-Cl-Ph and R² is Me. 86A Q² is2-F-4-Cl-Ph and R² is Cl. 87A Q² is 2-F-4-Cl-Ph and R² is Br. 88A Q² is2-F-4-Cl-Ph and R² is Et. 89A Q² is 2-F-4-Cl-Ph and R² is CN. 90A Q² is2,4-di-Cl-Ph and R² is Me. 91A Q² is 2,4-di-Cl-Ph and R² is Cl. 92A Q²is 2,4-di-Cl-Ph and R² is Br. 93A Q² is 2,4-di-Cl-Ph and R² is Et. 94AQ² is 2,4-di-Cl-Ph and R² is CN. 95A Q² is 2,6-di-Cl-Ph and R² is Me.96A Q² is 2,6-di-Cl-Ph and R² is Cl. 97A Q² is 2,6-di-Cl-Ph and R² isBr. 98A Q² is 2,6-di-Cl-Ph and R² is Et. 99A Q² is 2,6-di-Cl-Ph and R²is CN. 100A  Q² is 2-F-4-MeO-Ph and R² is Me. 101A  Q² is 2-F-4-MeO-Phand R² is Cl. 102A  Q² is 2-F-4-MeO-Ph and R² is Br. 103A  Q² is2-F-4-MeO-Ph and R² is Et. 104A  Q² is 2-F-4-MeO-Ph and R² is CN. 105A Q² is 2-F-4-EtO-Ph and R² is Me. 106A  Q² is 2-F-4-EtO-Ph and R² is Cl.107A  Q² is 2-F-4-EtO-Ph and R² is Br. 108A  Q² is 2-F-4-EtO-Ph and R²is Et. 109A  Q² is 2-F-4-EtO-Ph and R² is CN. 110A  Q² is 2-Cl-4-MeO-Phand R² is Me. 111A  Q² is 2-Cl-4-MeO-Ph and R² is Cl. 112A  Q² is2-Cl-4-MeO-Ph and R² is Br. 113A  Q² is 2-Cl-4-MeO-Ph and R² is Et.114A  Q² is 2-Cl-4-MeO-Ph and R² is CN. 115A  Q² is 2-Cl-4-EtO-Ph and R²is Me. 116A  Q² is 2-Cl-4-EtO-Ph and R² is Cl. 117A  Q² is 2-Cl-4-EtO-Phand R² is Br. 118A  Q² is 2-Cl-4-EtO-Ph and R² is Et. 119A  Q² is2-Cl-4-EtO-Ph and R² is CN. 120A  Q² is 2-Br-4-MeO-Ph and R² is Me.121A  Q² is 2-Br-4-MeO-Ph and R² is Cl. 122A  Q² is 2-Br-4-MeO-Ph and R²is Br. 123A  Q² is 2-Br-4-MeO-Ph and R² is Et. 124A  Q² is 2-Br-4-MeO-Phand R² is CN. 125A  Q² is 2-Br-4-EtO-Ph and R² is Me. 126A  Q² is2-Br-4-EtO-Ph and R² is Cl. 127A  Q² is 2-Br-4-EtO-Ph and R² is Br.128A  Q² is 2-Br-4-EtO-Ph and R² is Et. 129A  Q² is 2-Br-4-EtO-Ph and R²is CN. 130A  Q² is 2-F-4-CN-Ph and R² is Me. 131A  Q² is 2-F-4-CN-Ph andR² is Cl. 132A  Q² is 2-F-4-CN-Ph and R² is Br. 133A  Q² is 2-F-4-CN-Phand R² is Et. 134A  Q² is 2-F-4-CN-Ph and R² is CN. 135A  Q² is2-Cl-4-CN-Ph and R² is Me. 136A  Q² is 2-Cl-4-CN-Ph and R² is Cl. 137A Q² is 2-Cl-4-CN-Ph and R² is Br. 138A  Q² is 2-Cl-4-CN-Ph and R² is Et.139A  Q² is 2-Cl-4-CN-Ph and R² is CN. 140A  Q² is 2-Br-4-CN-Ph and R²is Me. 141A  Q² is 2-Br-4-CN-Ph and R² is Cl. 142A  Q² is 2-Br-4-CN-Phand R² is Br. 143A  Q² is 2-Br-4-CN-Ph and R² is Et. 144A  Q² is2-Br-4-CN-Ph and R² is CN. 145A  Q² is 3-Cl-2-pyridinyl and R² is Me.146A  Q² is 3-Cl-2-pyridinyl and R² is Cl. 147A  Q² is 3-Cl-2-pyridinyland R² is Br. 148A  Q² is 3-Cl-2-pyridinyl and R² is Et. 149A  Q² is3-Cl-2-pyridinyl and R² is CN. 150A  Q² is 3,5-di-Cl-2-pyridinyl and R²is Me. 151A  Q² is 3,5-di-Cl-2-pyridinyl and R² is Cl. 152A  Q² is3,5-di-Cl-2-pyridinyl and R² is Br. 153A  Q² is 3,5-di-Cl-2-pyridinyland R² is Et. 154A  Q² is 3,5-di-Cl-2-pyridinyl and R² is CN. 155A  Q²is 2-Cl-3-thienyl and R² is Me. 156A  Q² is 2-Cl-3-thienyl and R² is Cl.157A  Q² is 2-Cl-3-thienyl and R² is Br. 158A  Q² is 2-Cl-3-thienyl andR² is Et. 159A  Q² is 2-Cl-3-thienyl and R² is CN. 160A  Q² is2,5-di-Cl-3-thienyl and R² is Me. 161A  Q² is 2,5-di-Cl-3-thienyl and R²is Cl. 162A  Q² is 2,5-di-Cl-3-thienyand R² is Br. 163A  Q² is2,5-di-Cl-3-thienyl and R² is Et. 164A  Q² is 2,5-di-Cl-3-thienyl and R²is CN.

TABLE 2

(R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) 2-F2-F, 4-Cl 2-Cl, 4-MeO 2,4-di-Br, 6-F 2-F, 4-MeNH(CH₂)₃O 3-F 2-Cl, 4-F2-F, 4-MeO 2-Br, 4-Cl, 6-F 2-F, 4-Me₂N(CH₂)₃O 4-F 2-F, 4-Br 2-Cl, 4-EtO2-I, 4,6-di-F 2-Cl, 4-MeO(CH₂)₃O 2-Cl 2-Cl, 4-Br 2-F, 4-EtO 4-I,2,6-di-F 2,6-di-F, 4-MeNH(CH₂)₃O 3-Cl 2-Br, 4-Cl 2,4,5-tri-F 2,6-di-Cl,4-CN 2,6-di-F, 4-MeNH(CH₂)₃ 4-Cl 2-Br, 4-F 2,3,5-tri-F 2,6-di-F, 4-CN2,6-di-F, 4-Me₂N(CH₂)₃O 2-Br 2-I, 4-F 2,3,6-tri-F 2,6-di-Cl, 4-MeO2,6-di-F, 4-MeO(CH₂)₃O 3-Br 2-Me, 4-F 2,4,6-tri-F 2,6-di-F, 4-MeO2,6-di-F, 3-MeNH(CH₂)₃O 4-Br 2-Cl, 4-CN 2,4,6-tri-Cl 2,6-di-Cl, 4-EtO2,6-di-F, 3-MeNH(CH₂)₃ 4-Me 2-F, 4-CN 2-Cl, 4,6-di-F 2,6-di-F, 4-EtO2,6-di-F, 3-Me₂N(CH₂)₃O 2,6-di-F 2-Br, 4-CN 2,6-di-Cl, 4-F 2-Br, 4-F,6-Cl 2,6-di-F, 3-MeO(CH₂)₃O 2,4-di-F 2-CF₃, 4-F 2,4-di-Cl, 6-F 2-Cl,4-Br, 6-F 2-Cl-6-F, 5-MeNH(CH₂)₃O 2,4-di-Cl 2-Me, 4-MeO 4-Cl, 2,6-di-F4-MeNH(CH₂)₃O 2-Cl-6-F, 4-MeNH(CH₂)₃ 2,6-di-Cl 2-Me, 4-EtO 2-Br,4,6-di-F 4-Me₂N(CH₂)₃O 2-Cl-6-F, 4-Me₂N(CH₂)₃O 2,4-di-Me 2-Br, 4-MeO4-Br, 2,6-di-F 4-MeO(CH₂)₃O 2-Cl-6-F, 4-MeO(CH₂)₃O Q² is 2,6-di-F—Ph andR² is Me.

The present disclosure also includes Tables 1B through 164B, each ofwhich is constructed the same as Table 2 above, except that the rowheading in Table 2 (i.e. “Q² is 2,6-di-F-Ph and R² is Me”) is replacedwith the respective row heading shown below. For Example, in Table 1Bthe row heading is “Q² is 2,6-di-F-Ph and R² is Cl”, and (R³)_(p) is asdefined in Table 2 above. Thus, the first entry in Table 1B specificallydiscloses3-chloro-5-(2,6-difluorophenyl)-4-(2-fluorophenyl)-1-methyl-1H-pyrazole.Tables 2B through 164B are constructed similarly.

Table Row Heading  1B Q² is 2,6-di-F-Ph and R² is Cl.  2B Q² is2,6-di-F-Ph and R² is Br.  3B Q² is 2,6-di-F-Ph and R² is Et.  4B Q² is2,6-di-F-Ph and R² is CN.  5B Q² is 2,4-di-F-Ph and R² is Me.  6B Q² is2,4-di-F-Ph and R² is Cl.  7B Q² is 2,4-di-F-Ph and R² is Br.  8B Q² is2,4-di-F-Ph and R² is Et.  9B Q² is 2,4-di-F-Ph and R² is CN. 10B Q² is2,4,6-tri-F-Ph and R² is Me. 11B Q² is 2,4,6-tri-F-Ph and R² is Cl. 12BQ² is 2,4,6-tri-F-Ph and R² is Br. 13B Q² is 2,4,6-tri-F-Ph and R² isEt. 14B Q² is 2,4,6-tri-F-Ph and R² is CN. 15B Q² is 2,6-di-F-4-OMe-Phand R² is Me. 16B Q² is 2,6-di-F-4-OMe-Ph and R² is Cl. 17B Q² is2,6-di-F-4-OMe-Ph and R² is Br. 18B Q² is 2,6-di-F-4-OMe-Ph and R² isEt. 19B Q² is 2,6-di-F-4-OMe-Ph and R² is CN. 20B Q² is2,6-di-F-4-OEt-Ph and R² is Me. 21B Q² is 2,6-di-F-4-OEt-Ph and R² isCl. 22B Q² is 2,6-di-F-4-OEt-Ph and R² is Br. 23B Q² is2,6-di-F-4-OEt-Ph and R² is Et. 24B Q² is 2,6-di-F-4-OEt-Ph and R² isCN. 25B Q² is 2,6-di-F-4-CN-Ph and R² is Me. 26B Q² is 2,6-di-F-4-CN-Phand R² is Cl. 27B Q² is 2,6-di-F-4-CN-Ph and R² is Br. 28B Q² is2,6-di-F-4-CN-Ph and R² is Et. 29B Q² is 2,6-di-F-4-CN-Ph and R² is CN.30B Q² is 2-Cl-4-F-Ph and R² is Me. 31B Q² is 2-Cl-4-F-Ph and R² is Cl.32B Q² is 2-Cl-4-F-Ph and R² is Br. 33B Q² is 2-Cl-4-F-Ph and R² is Et.34B Q² is 2-Cl-4-F-Ph and R² is CN. 35B Q² is 2-Cl-6-F-Ph and R² is Me.36B Q² is 2-Cl-6-F-Ph and R² is Cl. 37B Q² is 2-Cl-6-F-Ph and R² is Br.38B Q² is 2-Cl-6-F-Ph and R² is Et. 39B Q² is 2-Cl-6-F-Ph and R² is CN.40B Q² is 2-Cl-4,6-di-F-Ph and R² is Me. 41B Q² is 2-Cl-4,6-di-F-Ph andR² is Cl. 42B Q² is 2-Cl-4,6-di-F-Ph and R² is Br. 43B Q² is2-Cl-4,6-di-F-Ph and R² is Et. 44B Q² is 2-Cl-4,6-di-F-Ph and R² is CN.45B Q² is 4-Cl-2,6-di-F-Ph and R² is Me. 46B Q² is 4-Cl-2,6-di-F-Ph andR² is Cl. 47B Q² is 4-Cl-2,6-di-F-Ph and R² is Br. 48B Q² is4-Cl-2,6-di-F-Ph and R² is Et. 49B Q² is 4-Cl-2,6-di-F-Ph and R² is CN.50B Q² is 2-Br-4-F-Ph and R² is Me. 51B Q² is 2-Br-4-F-Ph and R² is Cl.52B Q² is 2-Br-4-F-Ph and R² is Br. 53B Q² is 2-Br-4-F-Ph and R² is Et.54B Q² is 2-Br-4-F-Ph and R² is CN. 55B Q² is 2-Br-6-F-Ph and R² is Me.56B Q² is 2-Br-6-F-Ph and R² is Cl. 57B Q² is 2-Br-6-F-Ph and R² is Br.58B Q² is 2-Br-6-F-Ph and R² is Et. 59B Q² is 2-Br-6-F-Ph and R² is CN.60B Q² is 2-Me-4-F-Ph and R² is Me. 61B Q² is 2-Me-4-F-Ph and R² is Cl.62B Q² is 2-Me-4-F-Ph and R² is Br. 63B Q² is 2-Me-4-F-Ph and R² is Et.64B Q² is 2-Me-4-F-Ph and R² is CN. 65B Q² is 2-I-4-F-Ph and R² is Me.66B Q² is 2-I-4-F-Ph and R² is Cl. 67B Q² is 2-I-4-F-Ph and R² is Br.68B Q² is 2-I-4-F-Ph and R² is Et. 69B Q² is 2-I-4-F-Ph and R² is CN.70B Q² is 2-F-Ph and R² is Me. 71B Q² is 2-F-Ph and R² is Cl. 72B Q² is2-F-Ph and R² is Br. 73B Q² is 2-F-Ph and R² is Et. 74B Q² is 2-F-Ph andR² is CN. 75B Q² is 2-Cl-Ph and R² is Me. 76B Q² is 2-Cl-Ph and R² isCl. 77B Q² is 2-Cl-Ph and R² is Br. 78B Q² is 2-Cl-Ph and R² is Et. 79BQ² is 2-Cl-Ph an R² is CN. 80B Q² is 2-Br-Ph and R² is Me. 81B Q² is2-Br-Ph and R² is Cl. 82B Q² is 2-Br-Ph and R² is Br. 83B Q² is 2-Br-Phand R² is Et. 84B Q² is 2-Br-Ph and R² is CN. 85B Q² is 2-F-4-Cl-Ph andR² is Me. 86B Q² is 2-F-4-Cl-Ph and R² is Cl. 87B Q² is 2-F-4-Cl-Ph andR² is Br. 88B Q² is 2-F-4-Cl-Ph and R² is Et. 89B Q² is 2-F-4-Cl-Ph andR² is CN. 90B Q² is 2,4-di-Cl-Ph and R² is Me. 91B Q² is 2,4-di-Cl-Phand R² is Cl. 92B Q² is 2,4-di-Cl-Ph and R² is Br. 93B Q² is2,4-di-Cl-Ph and R² is Et. 94B Q² is 2,4-di-Cl-Ph and R² is CN. 95B Q²is 2,6-di-Cl-Ph and R² is Me. 96B Q² is 2,6-di-Cl-Ph and R² is Cl. 97BQ² is 2,6-di-Cl-Ph and R² is Br. 98B Q² is 2,6-di-Cl-Ph and R² is Et.99B Q² is 2,6-di-Cl-Ph and R² is CN. 100B  Q² is 2-F-4-MeO-Ph and R² isMe. 101B  Q² is 2-F-4-MeO-Ph and R² is Cl. 102B  Q² is 2-F-4-MeO-Ph andR² is Br. 103B  Q² is 2-F-4-MeO-Ph and R² is Et. 104B  Q² is2-F-4-MeO-Ph and R² is CN. 105B  Q² is 2-F-4-EtO-Ph and R² is Me. 106B Q² is 2-F-4-EtO-Ph and R² is Cl. 107B  Q² is 2-F-4-EtO-Ph and R² is Br.108B  Q² is 2-F-4-EtO-Ph and R² is Et. 109B  Q² is 2-F-4-EtO-Ph and R²is CN. 110B  Q² is 2-Cl-4-MeO-Ph and R² is Me. 111B  Q² is 2-Cl-4-MeO-Phand R² is Cl. 112B  Q² is 2-Cl-4-MeO-Ph and R² is Br. 113B  Q² is2-Cl-4-MeO-Ph and R² is Et. 114B  Q² is 2-Cl-4-MeO-Ph and R² is CN.115B  Q² is 2-Cl-4-EtO-Ph and R² is Me. 116B  Q² is 2-Cl-4-EtO-Ph and R²is Cl. 117B  Q² is 2-Cl-4-EtO-Ph and R² is Br. 118B  Q² is 2-Cl-4-EtO-Phand R² is Et. 119B  Q² is 2-Cl-4-EtO-Ph and R² is CN. 120B  Q² is2-Br-4-MeO-Ph and R² is Me. 121B  Q² is 2-Br-4-MeO-Ph and R² is Cl.122B  Q² is 2-Br-4-MeO-Ph and R² is Br. 123B  Q² is 2-Br-4-MeO-Ph and R²is Et. 124B  Q² is 2-Br-4-MeO-Ph and R² is CN. 125B  Q² is 2-Br-4-EtO-Phand R² is Me. 126B  Q² is 2-Br-4-EtO-Ph and R² is Cl. 127B  Q² is2-Br-4-EtO-Ph and R² is Br. 128B  Q² is 2-Br-4-EtO-Ph and R² is Et.129B  Q² is 2-Br-4-EtO-Ph and R² is CN. 130B  Q² is 2-F-4-CN-Ph and R²is Me. 131B  Q² is 2-F-4-CN-Ph and R² is Cl. 132B  Q² is 2-F-4-CN-Ph andR² is Br. 133B  Q² is 2-F-4-CN-Ph and R² is Et. 134B  Q² is 2-F-4-CN-Phand R² is CN. 135B  Q² is 2-Cl-4-CN-Ph and R² is Me. 136B  Q² is2-Cl-4-CN-Ph and R² is Cl. 137B  Q² is 2-Cl-4-CN-Ph and R² is Br. 138B Q² is 2-Cl-4-CN-Ph and R² is Et. 139B  Q² is 2-Cl-4-CN-Ph and R² is CN.140B  Q² is 2-Br-4-CN-Ph and R² is Me. 141B  Q² is 2-Br-4-CN-Ph and R²is Cl. 142B  Q² is 2-Br-4-CN-Ph and R² is Br. 143B  Q² is 2-Br-4-CN-Phand R² is Et. 144B  Q² is 2-Br-4-CN-Ph and R² is CN. 145B  Q² is3-Cl-2-pyridinyl and R² is Me. 146B  Q² is 3-Cl-2-pyridinyl and R² isCl. 147B  Q² is 3-Cl-2-pyridinyl and R² is Br. 148B  Q² is3-Cl-2-pyridinyl and R² is Et. 149B  Q² is 3-Cl-2-pyridinyl, and R² isCN. 150B  Q² is 3,5-di-Cl-2-pyridinyl and R² is Me. 151B  Q² is3,5-di-Cl-2-pyridinyl and R² is Cl. 152B  Q² is 3,5-di-Cl-2-pyridinyland R² is Br. 153B  Q² is 3,5-di-Cl-2-pyridinyl and R² is Et. 154B  Q²is 3,5-di-Cl-2-pyridinyl and R² is CN. 155B  Q² is 2-Cl-3-thienyl and R²is Me. 156B  Q² is 2-Cl-3-thienyl and R² is Cl. 157B  Q² is2-Cl-3-thienyl and R² is Br. 158B  Q² is 2-Cl-3-thienyl and R² is Et.159B  Q² is 2-Cl-3-thienyl and R² is CN. 160B  Q² is 2,5-di-Cl-3-thienyland R² is Me. 161B  Q² is 2,5-di-Cl-3-thienyl and R² is Cl. 162B  Q² is2,5-di-Cl-3-thienyl, and R² is Br. 163B  Q² is 2,5-di-Cl-3-thienyl andR² is Et. 164B  Q² is 2,5-di-Cl-3-thienyl and R² is CN.

TABLE 3

(R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) 2-F2-F, 4-Cl 2-Cl, 4-MeO 2,4-di-Br, 6-F 2-F, 4-MeNH(CH₂)₃O 3-F 2-Cl, 4-F2-F, 4-MeO 2-Br, 4-Cl, 6-F 2-F, 4-Me₂N(CH₂)₃O 4-F 2-F, 4-Br 2-Cl, 4-EtO2-I, 4,6-di-F 2-Cl, 4-MeO(CH₂)₃O 2-Cl 2-Cl, 4-Br 2-F, 4-EtO 4-I,2,6-di-F 2,6-di-F, 4-MeNH(CH₂)₃O 3-Cl 2-Br, 4-Cl 2,4,5-tri-F 2,6-di-Cl,4-CN 2,6-di-F, 4-MeNH(CH₂)₃ 4-Cl 2-Br, 4-F 2,3,5-tri-F 2,6-di-F, 4-CN2,6-di-F, 4-Me₂N(CH₂)₃O 2-Br 2-I, 4-F 2,3,6-tri-F 2,6-di-Cl, 4-MeO2,6-di-F, 4-MeO(CH₂)₃O 3-Br 2-Me, 4-F 2,4,6-tri-F 2,6-di-F, 4-MeO2,6-di-F, 3-MeNH(CH₂)₃O 4-Br 2-Cl, 4-CN 2,4,6-tri-Cl 2,6-di-Cl, 4-EtO2,6-di-F, 3-MeNH(CH₂)₃ 4-Me 2-F, 4-CN 2-Cl, 4,6-di-F 2,6-di-F, 4-EtO2,6-di-F, 3-Me₂N(CH₂)₃O 2,6-di-F 2-Br, 4-CN 2,6-di-Cl, 4-F 2-Br, 4-F,6-Cl 2,6-di-F, 3-MeO(CH₂)₃O 2,4-di-F 2-CF₃, 4-F 2,4-di-Cl, 6-F 2-Cl,4-Br, 6-F 2-Cl-6-F, 4-MeNH(CH₂)₃O 2,4-di-Cl 2-Me, 4-MeO 4-Cl, 2,6-di-F4-MeNH(CH₂)₃O 2-Cl-6-F, 4-MeNH(CH₂)₃ 2,6-di-Cl 2-Me, 4-EtO 2-Br,4,6-di-F 4-Me₂N(CH₂)₃O 2-Cl-6-F, 4-Me₂N(CH₂)₃O 2,4-di-Me 2-Br, 4-MeO4-Br, 2,6-di-F 4-MeO(CH₂)₃O 2-Cl-6-F, 4-MeO(CH₂)₃O Q² is 2,6-di-F—Ph andR² is Me.

The present disclosure also includes Tables 1C through 164C, each ofwhich is constructed the same as Table 3 above, except that the rowheading in Table 3 (i.e. “Q² is 2,6-di-F-Ph and R² is Me”) is replacedwith the respective row heading shown below. For Example, in Table 1Cthe row heading is “Q² is 2,6-di-F-Ph and R² is Cl”, and (R³)_(p) is asdefined in Table 3 above. Thus, the first entry in Table 1C specificallydiscloses3-chloro-5-(2,6-difluorophenyl)-4-[(2-fluorophenyl)thio]-1-methyl-1H-pyrazole.Tables 2C through 164C are constructed similarly.

Table Row Heading  1C Q² is 2,6-di-F-Ph and R² is Cl.  2C Q² is2,6-di-F-Ph and R² is Br.  3C Q² is 2,6-di-F-Ph and R² is Et.  4C Q² is2,6-di-F-Ph and R² is CN.  5C Q² is 2,4-di-F-Ph and R² is Me.  6C Q² is2,4-di-F-Ph and R² is Cl.  7C Q² is 2,4-di-F-Ph and R² is Br.  8C Q² is2,4-di-F-Ph and R² is Et.  9C Q² is 2,4-di-F-Ph and R² is CN. 10C Q² is2,4,6-tri-F-Ph and R² is Me. 11C Q² is 2,4,6-tri-F-Ph and R² is Cl. 12CQ² is 2,4,6-tri-F-Ph and R² is Br. 13C Q² is 2,4,6-tri-F-Ph and R² isEt. 14C Q² is 2,4,6-tri-F-Ph and R² is CN. 15C Q² is 2,6-di-F-4-OMe-Phand R² is Me. 16C Q² is 2,6-di-F-4-OMe-Ph and R² is Cl. 17C Q² is2,6-di-F-4-OMe-Ph and R² is Br. 18C Q² is 2,6-di-F-4-OMe-Ph and R² isEt. 19C Q² is 2,6-di-F-4-OMe-Ph and R² is CN. 20C Q² is2,6-di-F-4-OEt-Ph and R² is Me. 21C Q² is 2,6-di-F-4-OEt-Ph and R² isCl. 22C Q² is 2,6-di-F-4-OEt-Ph and R² is Br. 23C Q² is2,6-di-F-4-OEt-Ph and R² is Et. 24C Q² is 2,6-di-F-4-OEt-Ph and R² isCN. 25C Q² is 2,6-di-F-4-CN-Ph and R² is Me. 26C Q² is 2,6-di-F-4-CN-Phand R² is Cl. 27C Q² is 2,6-di-F-4-CN-Ph and R² is Br. 28C Q² is2,6-di-F-4-CN-Ph and R² is Et. 29C Q² is 2,6-di-F-4-CN-Ph and R² is CN.30C Q² is 2-Cl-4-F-Ph and R² is Me. 31C Q² is 2-Cl-4-F-Ph and R² is Cl.32C Q² is 2-Cl-4-F-Ph and R² is Br. 33C Q² is 2-Cl-4-F-Ph and R² is Et.34C Q² is 2-Cl-4-F-Ph and R² is CN. 35C Q² is 2-Cl-6-F-Ph and R² is Me.36C Q² is 2-Cl-6-F-Ph and R² is Cl. 37C Q² is 2-Cl-6-F-Ph and R² is Br.38C Q² is 2-Cl-6-F-Ph and R² is Et. 39C Q² is 2-Cl-6-F-Ph and R² is CN.40C Q² is 2-Cl-4,6-di-F-Ph and R² is Me. 41C Q² is 2-Cl-4,6-di-F-Ph andR² is Cl. 42C Q² is 2-Cl-4,6-di-F-Ph and R² is Br. 43C Q² is2-Cl-4,6-di-F-Ph and R² is Et. 44C Q² is 2-Cl-4,6-di-F-Ph and R² is CN.45C Q² is 4-Cl-2,6-di-F-Ph and R² is Me. 46C Q² is 4-Cl-2,6-di-F-Ph andR² is Cl. 47C Q² is 4-Cl-2,6-di-F-Ph and R² is Br. 48C Q² is4-Cl-2,6-di-F-Ph and R² is Et. 49C Q² is 4-Cl-2,6-di-F-Ph and R² is CN.50C Q² is 2-Br-4-F-Ph and R² is Me. 51C Q² is 2-Br-4-F-Ph and R² is Cl.52C Q² is 2-Br-4-F-Ph and R² is Br. 53C Q² is 2-Br-4-F-Ph and R² is Et.54C Q² is 2-Br-4-F-Ph and R² is CN. 55C Q² is 2-Br-6-F-Ph and R² is Me.56C Q² is 2-Br-6-F-Ph and R² is Cl. 57C Q² is 2-Br-6-F-Ph and R² is Br.58C Q² is 2-Br-6-F-Ph and R² is Et. 59C Q² is 2-Br-6-F-Ph and R² is CN.60C Q² is 2-Me-4-F-Ph and R² is Me. 61C Q² is 2-Me-4-F-Ph and R² is Cl.62C Q² is 2-Me-4-F-Ph and R² is Br. 63C Q² is 2-Me-4-F-Ph and R² is Et.64C Q² is 2-Me-4-F-Ph and R² is CN. 65C Q² is 2-I-4-F-Ph and R² is Me.66C Q² is 2-I-4-F-Ph and R² is Cl. 67C Q² is 2-I-4-F-Ph and R² is Br.68C Q² is 2-I-4-F-Ph and R² is Et. 69C Q² is 2-I-4-F-Ph and R² is CN.70C Q² is 2-F-Ph and R² is Me. 71C Q² is 2-F-Ph and R² is Cl. 72C Q² is2-F-Ph and R² is Br. 73C Q² is 2-F-Ph and R² is Et. 74C Q² is 2-F-Ph andR² is CN. 75C Q² is 2-Cl-Ph and R² is Me. 76C Q² is 2-Cl-Ph and R² isCl. 77C Q² is 2-Cl-Ph and R² is Br. 78C Q² is 2-Cl-Ph and R² is Et. 79CQ² is 2-Cl-Ph an R² is CN. 80C Q² is 2-Br-Ph and R² is Me. 81C Q² is2-Br-Ph and R² is Cl. 82C Q² is 2-Br-Ph and R² is Br. 83C Q² is 2-Br-Phand R² is Et. 84C Q² is 2-Br-Ph and R² is CN. 85C Q² is 2-F-4-Cl-Ph andR² is Me. 86C Q² is 2-F-4-Cl-Ph and R² is Cl. 87C Q² is 2-F-4-Cl-Ph andR² is Br. 88C Q² is 2-F-4-Cl-Ph and R² is Et. 89C Q² is 2-F-4-Cl-Ph andR² is CN. 90C Q² is 2,4-di-Cl-Ph and R² is Me. 91C Q² is 2,4-di-Cl-Phand R² is Cl. 92C Q² is 2,4-di-Cl-Ph and R² is Br. 93C Q² is2,4-di-Cl-Ph and R² is Et. 94C Q² is 2,4-di-Cl-Ph and R² is CN. 95C Q²is 2,6-di-Cl-Ph and R² is Me. 96C Q² is 2,6-di-Cl-Ph and R² is Cl. 97CQ² is 2,6-di-Cl-Ph and R² is Br. 98C Q² is 2,6-di-Cl-Ph and R² is Et.99C Q² is 2,6-di-Cl-Ph and R² is CN. 100C  Q² is 2-F-4-MeO-Ph and R² isMe. 101C  Q² is 2-F-4-MeO-Ph and R² is Cl. 102C  Q² is 2-F-4-MeO-Ph andR² is Br. 103C  Q² is 2-F-4-MeO-Ph and R² is Et. 104C  Q² is2-F-4-MeO-Ph and R² is CN. 105C  Q² is 2-F-4-EtO-Ph and R² is Me. 106C Q² is 2-F-4-EtO-Ph and R² is Cl. 107C  Q² is 2-F-4-EtO-Ph and R² is Br.108C  Q² is 2-F-4-EtO-Ph and R² is Et. 109C  Q² is 2-F-4-EtO-Ph and R²is CN. 110C  Q² is 2-Cl-4-MeO-Ph and R² is Me. 111C  Q² is 2-Cl-4-MeO-Phand R² is Cl. 112C  Q² is 2-Cl-4-MeO-Ph and R² is Br. 113C  Q² is2-Cl-4-MeO-Ph and R² is Et. 114C  Q² is 2-Cl-4-MeO-Ph and R² is CN.115C  Q² is 2-Cl-4-EtO-Ph and R² is Me. 116C  Q² is 2-Cl-4-EtO-Ph and R²is Cl. 117C  Q² is 2-Cl-4-EtO-Ph and R² is Br. 118C  Q² is 2-Cl-4-EtO-Phand R² is Et. 119C  Q² is 2-Cl-4-EtO-Ph and R² is CN. 120C  Q² is2-Br-4-MeO-Ph and R² is Me. 121C  Q² is 2-Br-4-MeO-Ph and R² is Cl.122C  Q² is 2-Br-4-MeO-Ph and R² is Br. 123C  Q² is 2-Br-4-MeO-Ph and R²is Et. 124C  Q² is 2-Br-4-MeO-Ph and R² is CN. 125C  Q² is 2-Br-4-EtO-Phand R² is Me. 126C  Q² is 2-Br-4-EtO-Ph and R² is Cl. 127C  Q² is2-Br-4-EtO-Ph and R² is Br. 128C  Q² is 2-Br-4-EtO-Ph and R² is Et.129C  Q² is 2-Br-4-EtO-Ph and R² is CN. 130C  Q² is 2-F-4-CN-Ph and R²is Me. 131C  Q² is 2-F-4-CN-Ph and R² is Cl. 132C  Q² is 2-F-4-CN-Ph andR² is Br. 133C  Q² is 2-F-4-CN-Ph and R² is Et. 134C  Q² is 2-F-4-CN-Phand R² is CN. 135C  Q² is 2-Cl-4-CN-Ph and R² is Me. 136C  Q² is2-Cl-4-CN-Ph and R² is Cl. 137C  Q² is 2-Cl-4-CN-Ph and R² is Br. 138C Q² is 2-Cl-4-CN-Ph and R² is Et. 139C  Q² is 2-Cl-4-CN-Ph and R² is CN.140C  Q² is 2-Br-4-CN-Ph and R² is Me. 141C  Q² is 2-Br-4-CN-Ph and R²is Cl. 142C  Q² is 2-Br-4-CN-Ph and R² is Br. 143C  Q² is 2-Br-4-CN-Phand R² is Et. 144C  Q² is 2-Br-4-CN-Ph and R² is CN. 145C  Q² is3-Cl-2-pyridinyl and R² is Me. 146C  Q² is 3-Cl-2-pyridinyl and R² isCl. 147C  Q² is 3-Cl-2-pyridinyl and R² is Br. 148C  Q² is3-Cl-2-pyridinyl and R² is Et. 149C  Q² is 3-Cl-2-pyridinyl and R² isCN. 150C  Q² is 3,5-di-Cl-2-pyridinyl and R² is Me. 151C  Q² is3,5-di-Cl-2-pyridinyl and R² is Cl. 152C  Q² is 3,5-di-Cl-2-pyridinyland R² is Br. 153C  Q² is 3,5-di-Cl-2-pyridinyl and R² is Et. 154C  Q²is 3,5-di-Cl-2-pyridinyl and R² is CN. 155C  Q² is 2-Cl-3-thienyl and R²is Me. 156C  Q² is 2-Cl-3-thienyl and R² is Cl. 157C  Q² is2-Cl-3-thienyl and R² is Br. 158C  Q² is 2-Cl-3-thienyl and R² is Et.159C  Q² is 2-Cl-3-thienyl and R² is CN. 160C  Q² is 2,5-di-Cl-3-thienyland R² is Me. 161C  Q² is 2,5-di-Cl-3-thienyl and R² is Cl. 162C  Q² is2,5-di-Cl-3-thienyl and R² is Br. 163C  Q² is 2,5-di-Cl-3-thienyl and R²is Et. 164C  Q² is 2,5-di-Cl-3-thienyl and R² is CN.

TABLE 4

(R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) 2-F2-F, 4-Cl 2-Cl, 4-MeO 2,4-di-Br, 6-F 2-F, 4-MeNH(CH₂)₃O 3-F 2-Cl, 4-F2-F, 4-MeO 2-Br, 4-Cl, 6-F 2-F, 4-Me₂N(CH₂)₃O 4-F 2-F, 4-Br 2-Cl, 4-EtO2-I, 4,6-di-F 2-Cl, 4-MeO(CH₂)₃O 2-Cl 2-Cl, 4-Br 2-F, 4-EtO 4-I,2,6-di-F 2,6-di-F, 4-MeNH(CH₂)₃O 3-Cl 2-Br, 4-Cl 2,4,5-tri-F 2,6-di-Cl,4-CN 2,6-di-F, 4-MeNH(CH₂)₃ 4-Cl 2-Br, 4-F 2,3,5-tri-F 2,6-di-F, 4-CN2,6-di-F, 4-Me₂N(CH₂)₃O 2-Br 2-I, 4-F 2,3,6-tri-F 2,6-di-Cl, 4-MeO2,6-di-F, 4-MeO(CH₂)₃O 3-Br 2-Me, 4-F 2,4,6-tri-F 2,6-di-F, 4-MeO2,6-di-F, 3-MeNH(CH₂)₃O 4-Br 2-Cl, 4-CN 2,4,6-tri-Cl 2,6-di-Cl, 4-EtO2,6-di-F, 3-MeNH(CH₂)₃ 4-Me 2-F, 4-CN 2-Cl, 4,6-di-F 2,6-di-F, 4-EtO2,6-di-F, 3-Me₂N(CH₂)₃O 2,6-di-F 2-Br, 4-CN 2,6-di-Cl, 4-F 2-Br, 4-F,6-Cl 2,6-di-F, 3-MeO(CH₂)₃O 2,4-di-F 2-CF₃, 4-F 2,4-di-Cl, 6-F 2-Cl,4-Br, 6-F 2-Cl-6-F, 5-MeNH(CH₂)₃O 2,4-di-Cl 2-Me, 4-MeO 4-Cl, 2,6-di-F4-MeNH(CH₂)₃O 2-Cl-6-F, 4-MeNH(CH₂)₃ 2,6-di-Cl 2-Me, 4-EtO 2-Br,4,6-di-F 4-Me₂N(CH₂)₃O 2-Cl-6-F, 4-Me₂N(CH₂)₃O 2,4-di-Me 2-Br, 4-MeO4-Br, 2,6-di-F 4-MeO(CH₂)₃O 2-Cl-6-F, 4-MeO(CH₂)₃O Q² is 2,6-di-F—Ph andR² is Me.

The present disclosure also includes Tables 1D through 164D, each ofwhich is constructed the same as Table 4 above, except that the rowheading in Table 4 (i.e. “Q² is 2,6-di-F-Ph and R² is Me”) is replacedwith the respective row heading shown below. For Example, in Table 1Dthe row heading is “Q² is 2,6-di-F-Ph and R² is Cl”, and (R³)_(p) is asdefined in Table 4 above. Thus, the first entry in Table 1D specificallydiscloses3-chloro-5-(2,6-difluorophenyl)-α-(2-fluorophenyl)-1-methyl-1H-pyrazole-4-methanol.Tables 2D through 164D are constructed similarly.

Table Row Heading  1D Q² is 2,6-di-F-Ph and R² is Cl.  2D Q² is2,6-di-F-Ph and R² is Br.  3D Q² is 2,6-di-F-Ph and R² is Et.  4D Q² is2,6-di-F-Ph and R² is CN.  5D Q² is 2,4-di-F-Ph and R² is Me.  6D Q² is2,4-di-F-Ph and R² is Cl.  7D Q² is 2,4-di-F-Ph and R² is Br.  8D Q² is2,4-di-F-Ph and R² is Et.  9D Q² is 2,4-di-F-Ph and R² is CN. 10D Q² is2,4,6-tri-F-Ph and R² is Me. 11D Q² is 2,4,6-tri-F-Ph and R² is Cl. 12DQ² is 2,4,6-tri-F-Ph and R² is Br. 13D Q² is 2,4,6-tri-F-Ph and R² isEt. 14D Q² is 2,4,6-tri-F-Ph and R² is CN. 15D Q² is 2,6-di-F-4-OMe-Phand R² is Me. 16D Q² is 2,6-di-F-4-OMe-Ph and R² is Cl. 17D Q² is2,6-di-F-4-OMe-Ph and R² is Br. 18D Q² is 2,6-di-F-4-OMe-Ph and R² is Et19D Q² is 2,6-di-F-4-OMe-Ph and R² is CN 20D Q² is 2,6-di-F-4-OEt-Ph andR² is Me. 21D Q² is 2,6-di-F-4-OEt-Ph and R² is Cl. 22D Q² is2,6-di-F-4-OEt-Ph and R² is Br. 23D Q² is 2,6-di-F-4-OEt-Ph and R² isEt. 24D Q² is 2,6-di-F-4-OEt-Ph and R² is CN. 25D Q² is 2,6-di-F-4-CN-Phand R² is Me. 26D Q² is 2,6-di-F-4-CN-Ph and R² is Cl. 27D Q² is2,6-di-F-4-CN-Ph and R² is Br. 28D Q² is 2,6-di-F-4-CN-Ph and R² is Et.29D Q² is 2,6-di-F-4-CN-Ph and R² is CN. 30D Q² is 2-Cl-4-F-Ph and R² isMe. 31D Q² is 2-Cl-4-F-Ph and R² is Cl. 32D Q² is 2-Cl-4-F-Ph and R² isBr. 33D Q² is 2-Cl-4-F-Ph and R² is Et. 34D Q² is 2-Cl-4-F-Ph and R² isCN. 35D Q² is 2-Cl-6-F-Ph and R² is Me. 36D Q² is 2-Cl-6-F-Ph and R² isCl. 37D Q² is 2-Cl-6-F-Ph and R² is Br. 38D Q² is 2-Cl-6-F-Ph and R² isEt. 39D Q² is 2-Cl-6-F-Ph and R² is CN. 40D Q² is 2-Cl-4,6-di-F-Ph andR² is Me. 41D Q² is 2-Cl-4,6-di-F-Ph and R² is Cl. 42D Q² is2-Cl-4,6-di-F-Ph and R² is Br. 43D Q² is 2-Cl-4,6-di-F-Ph and R² is Et.44D Q² is 2-Cl-4,6-di-F-Ph and R² is CN. 45D Q² is 4-Cl-2,6-di-F-Ph andR² is Me. 46D Q² is 4-Cl-2,6-di-F-Ph and R² is Cl. 47D Q² is4-Cl-2,6-di-F-Ph and R² is Br. 48D Q² is 4-Cl-2,6-di-F-Ph and R² is Et.49D Q² is 4-Cl-2,6-di-F-Ph and R² is CN. 50D Q² is 2-Br-4-F-Ph and R² isMe. 51D Q² is 2-Br-4-F-Ph and R² is Cl. 52D Q² is 2-Br-4-F-Ph and R² isBr. 53D Q² is 2-Br-4-F-Ph and R² is Et. 54D Q² is 2-Br-4-F-Ph and R² isCN. 55D Q² is 2-Br-6-F-Ph and R² is Me. 56D Q² is 2-Br-6-F-Ph and R² isCl. 57D Q² is 2-Br-6-F-Ph and R² is Br. 58D Q² is 2-Br-6-F-Ph and R² isEt. 59D Q² is 2-Br-6-F-Ph and R² is CN. 60D Q² is 2-Me-4-F-Ph and R² isMe. 61D Q² is 2-Me-4-F-Ph and R² is Cl. 62D Q² is 2-Me-4-F-Ph and R² isBr. 63D Q² is 2-Me-4-F-Ph and R² is Et. 64D Q² is 2-Me-4-F-Ph and R² isCN. 65D Q² is 2-I-4-F-Ph and R² is Me. 66D Q² is 2-I-4-F-Ph and R² isCl. 67D Q² is 2-I-4-F-Ph and R² is Br. 68D Q² is 2-I-4-F-Ph and R² isEt. 69D Q² is 2-I-4-F-Ph and R² is CN. 70D Q² is 2-F-Ph and R² is Me.71D Q² is 2-F-Ph and R² is Cl. 72D Q² is 2-F-Ph and R² is Br. 73D Q² is2-F-Ph and R² is Et. 74D Q² is 2-F-Ph and R² is CN. 75D Q² is 2-Cl-Phand R² is Me. 76D Q² is 2-Cl-Ph and R² is Cl. 77D Q² is 2-Cl-Ph and R²is Br. 78D Q² is 2-Cl-Ph and R² is Et. 79D Q² is 2-Cl-Ph an R² is CN 80DQ² is 2-Br-Ph and R² is Me. 81D Q² is 2-Br-Ph and R² is Cl. 82D Q² is2-Br-Ph and R² is Br. 83D Q² is 2-Br-Ph and R² is Et. 84D Q² is 2-Br-Phand R² is CN. 85D Q² is 2-F-4-Cl-Ph and R² is Me. 86D Q² is 2-F-4-Cl-Phand R² is Cl. 87D Q² is 2-F-4-Cl-Ph and R² is Br. 88D Q² is 2-F-4-Cl-Phand R² is Et. 89D Q² is 2-F-4-Cl-Ph and R² is CN. 90D Q² is 2,4-di-Cl-Phand R² is Me. 91D Q² is 2,4-di-Cl-Ph and R² is Cl. 92D Q² is2,4-di-Cl-Ph and R² is Br. 93D Q² is 2,4-di-Cl-Ph and R² is Et. 94D Q²is 2,4-di-Cl-Ph and R² is CN. 95D Q² is 2,6-di-Cl-Ph and R² is Me. 96DQ² is 2,6-di-Cl-Ph and R² is Cl. 97D Q² is 2,6-di-Cl-Ph and R² is Br.98D Q² is 2,6-di-Cl-Ph and R² is Et. 99D Q² is 2,6-di-Cl-Ph and R² isCN. 100D  Q² is 2-F-4-MeO-Ph and R² is Me. 101D  Q² is 2-F-4-MeO-Ph andR² is Cl. 102D  Q² is 2-F-4-MeO-Ph and R² is Br. 103D  Q² is2-F-4-MeO-Ph and R² is Et. 104D  Q² is 2-F-4-MeO-Ph and R² is CN. 105D Q² is 2-F-4-EtO-Ph and R² is Me. 106D  Q² is 2-F-4-EtO-Ph and R² is Cl.107D  Q² is 2-F-4-EtO-Ph and R² is Br. 108D  Q² is 2-F-4-EtO-Ph and R²is Et. 109D  Q² is 2-F-4-EtO-Ph and R² is CN. 110D  Q² is 2-Cl-4-MeO-Phand R² is Me. 111D  Q² is 2-Cl-4-MeO-Ph and R² is Cl. 112D  Q² is2-Cl-4-MeO-Ph and R² is Br. 113D  Q² is 2-Cl-4-MeO-Ph and R² is Et.114D  Q² is 2-Cl-4-MeO-Ph and R² is CN. 115D  Q² is 2-Cl-4-EtO-Ph and R²is Me. 116D  Q² is 2-Cl-4-EtO-Ph and R² is Cl. 117D  Q² is 2-Cl-4-EtO-Phand R² is Br. 118D  Q² is 2-Cl-4-EtO-Ph and R² is Et. 119D  Q² is2-Cl-4-EtO-Ph and R² is CN. 120D  Q² is 2-Br-4-MeO-Ph and R² is Me.121D  Q² is 2-Br-4-MeO-Ph and R² is Cl. 122D  Q² is 2-Br-4-MeO-Ph and R²is Br. 123D  Q² is 2-Br-4-MeO-Ph and R² is Et. 124D  Q² is 2-Br-4-MeO-Phand R² is CN. 125D  Q² is 2-Br-4-EtO-Ph and R² is Me. 126D  Q² is2-Br-4-EtO-Ph and R² is Cl. 127D  Q² is 2-Br-4-EtO-Ph and R² is Br.128D  Q² is 2-Br-4-EtO-Ph and R² is Et. 129D  Q² is 2-Br-4-EtO-Ph and R²is CN. 130D  Q² is 2-F-4-CN-Ph and R² is Me. 131D  Q² is 2-F-4-CN-Ph andR² is Cl. 132D  Q² is 2-F-4-CN-Ph and R² is Br. 133D  Q² is 2-F-4-CN-Phand R² is Et. 134D  Q² is 2-F-4-CN-Ph and R² is CN. 135D  Q² is2-Cl-4-CN-Ph and R² is Me. 136D  Q² is 2-Cl-4-CN-Ph and R² is Cl. 137D Q² is 2-Cl-4-CN-Ph and R² is Br. 138D  Q² is 2-Cl-4-CN-Ph and R² is Et.139D  Q² is 2-Cl-4-CN-Ph and R² is CN. 140D  Q² is 2-Br-4-CN-Ph and R²is Me. 141D  Q² is 2-Br-4-CN-Ph and R² is Cl. 142D  Q² is 2-Br-4-CN-Phand R² is Br. 143D  Q² is 2-Br-4-CN-Ph and R² is Et. 144D  Q² is2-Br-4-CN-Ph and R² is CN. 145D  Q² is 3-Cl-2-pyridinyl and R² is Me.146D  Q² is 3-Cl-2-pyridinyl and R² is Cl. 147D  Q² is 3-Cl-2-pyridinyland R² is Br. 148D  Q² is 3-Cl-2-pyridinyl and R² is Et. 149D  Q² is3-Cl-2-pyridinyl and R² is CN. 150D  Q² is 3,5-di-Cl-2-pyridinyl and R²is Me. 151D  Q² is 3,5-di-Cl-2-pyridinyl and R² is Cl. 152D  Q² is3,5-di-Cl-2-pyridinyl and R² is Br. 153D  Q² is 3,5-di-Cl-2-pyridinyland R² is Et. 154D  Q² is 3,5-di-Cl-2-pyridinyl and R² is CN. 155D  Q²is 2-Cl-3-thienyl and R² is Me. 156D  Q² is 2-Cl-3-thienyl and R² is Cl.157D  Q² is 2-Cl-3-thienyl and R² is Br. 158D  Q² is 2-Cl-3-thienyl andR² is Et. 159D  Q² is 2-Cl-3-thienyl and R² is CN. 160D  Q² is2,5-di-Cl-3-thienyl and R² is Me. 161D  Q² is 2,5-di-Cl-3-thienyl and R²is Cl. 162D  Q² is 2,5-di-Cl-3-thienyl and R² is Br. 163D  Q² is2,5-di-Cl-3-thienyl and R² is Et. 164D  Q² is 2,5-di-Cl-3-thienyl and R²is CN.

TABLE 5

(R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) (R^(3a))_(p) 2-F2-F, 4-Cl 2-Cl, 4-MeO 2,4-di-Br, 6-F 2-F, 4-MeNH(CH₂)₃O 3-F 2-Cl, 4-F2-F, 4-MeO 2-Br, 4-Cl, 6-F 2-F, 4-Me₂N(CH₂)₃O 4-F 2-F, 4-Br 2-Cl, 4-EtO2-I, 4,6-di-F 2-Cl, 4-MeO(CH₂)₃O 2-Cl 2-Cl, 4-Br 2-F, 4-EtO 4-I,2,6-di-F 2,6-di-F, 4-MeNH(CH₂)₃O 3-Cl 2-Br, 4-Cl 2,4,5-tri-F 2,6-di-Cl,4-CN 2,6-di-F, 4-MeNH(CH₂)₃ 4-Cl 2-Br, 4-F 2,3,5-tri-F 2,6-di-F, 4-CN2,6-di-F, 4-Me₂N(CH₂)₃O 2-Br 2-I, 4-F 2,3,6-tri-F 2,6-di-Cl, 4-MeO2,6-di-F, 4-MeO(CH₂)₃O 3-Br 2-Me, 4-F 2,4,6-tri-F 2,6-di-F, 4-MeO2,6-di-F, 3-MeNH(CH₂)₃O 4-Br 2-Cl, 4-CN 2,4,6-tri-Cl 2,6-di-Cl, 4-EtO2,6-di-F, 3-MeNH(CH₂)₃ 4-Me 2-F, 4-CN 2-Cl, 4,6-di-F 2,6-di-F, 4-EtO2,6-di-F, 3-Me₂N(CH₂)₃O 2,6-di-F 2-Br, 4-CN 2,6-di-Cl, 4-F 2-Br, 4-F,6-Cl 2,6-di-F, 3-MeO(CH₂)₃O 2,4-di-F 2-CF₃, 4-F 2,4-di-Cl, 6-F 2-Cl,4-Br, 6-F 2-Cl-6-F, 5-MeNH(CH₂)₃O 2,4-di-Cl 2-Me, 4-MeO 4-Cl, 2,6-di-F4-MeNH(CH₂)₃O 2-Cl-6-F, 4-MeNH(CH₂)₃ 2,6-di-Cl 2-Me, 4-EtO 2-Br,4,6-di-F 4-Me₂N(CH₂)₃O 2-Cl-6-F, 4-Me₂N(CH₂)₃O 2,4-di-Me 2-Br, 4-MeO4-Br, 2,6-di-F 4-MeO(CH₂)₃O 2-Cl-6-F, 4-MeO(CH₂)₃O Q² is 2,6-di-F—Ph andR² is Me.

The present disclosure also includes Tables 1E through 164E, each ofwhich is constructed the same as Table 5 above, except that the rowheading in Table 5 (i.e. “Q² is 2,6-di-F-Ph and R² is Me”) is replacedwith the respective row heading shown below. For Example, in Table 1Ethe row heading is “Q² is 2,6-di-F-Ph and R² is Cl”, and (R³)_(p) is asdefined in Table 5 above. Thus, the first entry in Table 1E specificallydiscloses(3-chloro-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazol-4-yl](2-fluorophenyl)methanol.Tables 2E through 164E are constructed similarly.

Table Row Heading  1E Q² is 2,6-di-F-Ph and R² is Cl.  2E Q² is2,6-di-F-Ph and R² is Br.  3E Q² is 2,6-di-F-Ph and R² is Et.  4E Q² is2,6-di-F-Ph and R² is CN.  5E Q² is 2,4-di-F-Ph and R² is Me.  6E Q² is2,4-di-F-Ph and R² is Cl.  7E Q² is 2,4-di-F-Ph and R² is Br.  8E Q² is2,4-di-F-Ph and R² is Et.  9E Q² is 2,4-di-F-Ph and R² is CN. 10E Q² is2,4,6-tri-F-Ph and R² is Me. 11E Q² is 2,4,6-tri-F-Ph and R² is Cl. 12EQ² is 2,4,6-tri-F-Ph and R² is Br. 13E Q² is 2,4,6-tri-F-Ph and R² isEt. 14E Q² is 2,4,6-tri-F-Ph and R² is CN. 15E Q² is 2,6-di-F-4-OMe-Phand R² is Me. 16E Q² is 2,6-di-F-4-OMe-Ph and R² is Cl. 17E Q² is2,6-di-F-4-OMe-Ph and R² is Br. 18E Q² is 2,6-di-F-4-OMe-Ph and R² is Et19E Q² is 2,6-di-F-4-OMe-Ph and R² is CN 20E Q² is 2,6-di-F-4-OEt-Ph andR² is Me. 21E Q² is 2,6-di-F-4-OEt-Ph and R² is Cl. 22E Q² is2,6-di-F-4-OEt-Ph and R² is Br. 23E Q² is 2,6-di-F-4-OEt-Ph and R² isEt. 24E Q² is 2,6-di-F-4-OEt-Ph and R² is CN. 25E Q² is 2,6-di-F-4-CN-Phand R² is Me. 26E Q² is 2,6-di-F-4-CN-Ph and R² is Cl. 27E Q² is2,6-di-F-4-CN-Ph and R² is Br. 28E Q² is 2,6-di-F-4-CN-Ph and R² is Et.29E Q² is 2,6-di-F-4-CN-Ph and R² is CN. 30E Q² is 2-Cl-4-F-Ph and R² isMe. 31E Q² is 2-Cl-4-F-Ph and R² is Cl. 32E Q² is 2-Cl-4-F-Ph and R² isBr. 33E Q² is 2-Cl-4-F-Ph and R² is Et. 34E Q² is 2-Cl-4-F-Ph and R² isCN. 35E Q² is 2-Cl-6-F-Ph and R² is Me. 36E Q² is 2-Cl-6-F-Ph and R² isCl. 37E Q² is 2-Cl-6-F-Ph and R² is Br. 38E Q² is 2-Cl-6-F-Ph and R² isEt. 39E Q² is 2-Cl-6-F-Ph and R² is CN. 40E Q² is 2-Cl-4,6-di-F-Ph andR² is Me. 41E Q² is 2-Cl-4,6-di-F-Ph and R² is Cl. 42E Q² is2-Cl-4,6-di-F-Ph and R² is Br. 43E Q² is 2-Cl-4,6-di-F-Ph and R² is Et.44E Q² is 2-Cl-4,6-di-F-Ph and R² is CN. 45E Q² is 4-Cl-2,6-di-F-Ph andR² is Me. 46E Q² is 4-Cl-2,6-di-F-Ph and R² is Cl. 47E Q² is4-Cl-2,6-di-F-Ph and R² is Br. 48E Q² is 4-Cl-2,6-di-F-Ph and R² is Et.49E Q² is 4-Cl-2,6-di-F-Ph and R² is CN. 50E Q² is 2-Br-4-F-Ph and R² isMe. 51E Q² is 2-Br-4-F-Ph and R² is Cl. 52E Q² is 2-Br-4-F-Ph and R² isBr. 53E Q² is 2-Br-4-F-Ph and R² is Et. 54E Q² is 2-Br-4-F-Ph and R² isCN. 55E Q² is 2-Br-6-F-Ph and R² is Me. 56E Q² is 2-Br-6-F-Ph and R² isCl. 57E Q² is 2-Br-6-F-Ph and R² is Br. 58E Q² is 2-Br-6-F-Ph and R² isEt. 59E Q² is 2-Br-6-F-Ph and R² is CN. 60E Q² is 2-Me-4-F-Ph and R² isMe. 61E Q² is 2-Me-4-F-Ph and R² is Cl. 62E Q² is 2-Me-4-F-Ph and R² isBr. 63E Q² is 2-Me-4-F-Ph and R² is Et. 64E Q² is 2-Me-4-F-Ph and R² isCN. 65E Q² is 2-I-4-F-Ph and R² is Me. 66E Q² is 2-I-4-F-Ph and R² isCl. 67E Q² is 2-I-4-F-Ph and R² is Br. 68E Q² is 2-I-4-F-Ph and R² isEt. 69E Q² is 2-I-4-F-Ph and R² is CN. 70E Q² is 2-F-Ph and R² is Me.71E Q² is 2-F-Ph and R² is Cl. 72E Q² is 2-F-Ph and R² is Br. 73E Q² is2-F-Ph and R² is Et. 74E Q² is 2-F-Ph and R² is CN. 75E Q² is 2-Cl-Phand R² is Me. 76E Q² is 2-Cl-Ph and R² is Cl. 77E Q² is 2-Cl-Ph and R²is Br. 78E Q² is 2-Cl-Ph and R² is Et. 79E Q² is 2-Cl-Ph an R² is CN.80E Q² is 2-Br-Ph and R² is Me. 81E Q² is 2-Br-Ph and R² is Cl. 82E Q²is 2-Br-Ph and R² is Br. 83E Q² is 2-Br-Ph and R² is Et. 84E Q² is2-Br-Ph and R² is CN. 85E Q² is 2-F-4-Cl-Ph and R² is Me. 86E Q² is2-F-4-Cl-Ph and R² is Cl. 87E Q² is 2-F-4-Cl-Ph and R² is Br. 88E Q² is2-F-4-Cl-Ph and R² is Et. 89E Q² is 2-F-4-Cl-Ph and R² is CN. 90E Q² is2,4-di-Cl-Ph and R² is Me. 91E Q² is 2,4-di-Cl-Ph and R² is Cl. 92E Q²is 2,4-di-Cl-Ph and R² is Br. 93E Q² is 2,4-di-Cl-Ph and R² is Et. 94EQ² is 2,4-di-Cl-Ph and R² is CN. 95E Q² is 2,6-di-Cl-Ph and R² is Me.96E Q² is 2,6-di-Cl-Ph and R² is Cl. 97E Q² is 2,6-di-Cl-Ph and R² isBr. 98E Q² is 2,6-di-Cl-Ph and R² is Et. 99E Q² is 2,6-di-Cl-Ph and R²is CN. 100E  Q² is 2-F-4-MeO-Ph and R² is Me. 101E  Q² is 2-F-4-MeO-Phand R² is Cl. 102E  Q² is 2-F-4-MeO-Ph and R² is Br. 103E  Q² is2-F-4-MeO-Ph and R² is Et. 104E  Q² is 2-F-4-MeO-Ph and R² is CN. 105E Q² is 2-F-4-EtO-Ph and R² is Me. 106E  Q² is 2-F-4-EtO-Ph and R² is Cl.107E  Q² is 2-F-4-EtO-Ph and R² is Br. 108E  Q² is 2-F-4-EtO-Ph and R²is Et. 109E  Q² is 2-F-4-EtO-Ph and R² is CN. 110E  Q² is 2-Cl-4-MeO-Phand R² is Me. 111E  Q² is 2-Cl-4-MeO-Ph and R² is Cl. 112E  Q² is2-Cl-4-MeO-Ph and R² is Br. 113E  Q² is 2-Cl-4-MeO-Ph and R² is Et.114E  Q² is 2-Cl-4-MeO-Ph and R² is CN. 115E  Q² is 2-Cl-4-EtO-Ph and R²is Me. 116E  Q² is 2-Cl-4-EtO-Ph and R² is Cl. 117E  Q² is 2-Cl-4-EtO-Phand R² is Br. 118E  Q² is 2-Cl-4-EtO-Ph and R² is Et. 119E  Q² is2-Cl-4-EtO-Ph and R² is CN. 120E  Q² is 2-Br-4-MeO-Ph and R² is Me.121E  Q² is 2-Br-4-MeO-Ph and R² is Cl. 122E  Q² is 2-Br-4-MeO-Ph and R²is Br. 123E  Q² is 2-Br-4-MeO-Ph and R² is Et. 124E  Q² is 2-Br-4-MeO-Phand R² is CN. 125E  Q² is 2-Br-4-EtO-Ph and R² is Me. 126E  Q² is2-Br-4-EtO-Ph and R² is Cl. 127E  Q² is 2-Br-4-EtO-Ph and R² is Br.128E  Q² is 2-Br-4-EtO-Ph and R² is Et. 129E  Q² is 2-Br-4-EtO-Ph and R²is CN. 130E  Q² is 2-F-4-CN-Ph and R² is Me. 131E  Q² is 2-F-4-CN-Ph andR² is Cl. 132E  Q² is 2-F-4-CN-Ph and R² is Br. 133E  Q² is 2-F-4-CN-Phand R² is Et. 134E  Q² is 2-F-4-CN-Ph and R² is CN. 135E  Q² is2-Cl-4-CN-Ph and R² is Me. 136E  Q² is 2-Cl-4-CN-Ph and R² is Cl. 137E Q² is 2-Cl-4-CN-Ph and R² is Br. 138E  Q² is 2-Cl-4-CN-Ph and R² is Et.139E  Q² is 2-Cl-4-CN-Ph and R² is CN. 140E  Q² is 2-Br-4-CN-Ph and R²is Me. 141E  Q² is 2-Br-4-CN-Ph and R² is Cl. 142E  Q² is 2-Br-4-CN-Phand R² is Br. 143E  Q² is 2-Br-4-CN-Ph and R² is Et. 144E  Q² is2-Br-4-CN-Ph and R² is CN. 145E  Q² is 3-Cl-2-pyridinyl and R² is Me.146E  Q² is 3-Cl-2-pyridinyl and R² is Cl. 147E  Q² is 3-Cl-2-pyridinyland R² is Br. 148E  Q² is 3-Cl-2-pyridinyl and R² is Et. 149E  Q² is3-Cl-2-pyridinyl and R² is CN. 150E  Q² is 3,5-di-Cl-2-pyridinyl and R²is Me. 151E  Q² is 3,5-di-Cl-2-pyridinyl and R² is Cl. 152E  Q² is3,5-di-Cl-2-pyridinyl and R² is Br. 153E  Q² is 3,5-di-Cl-2-pyridinyland R² is Et. 154E  Q² is 3,5-di-Cl-2-pyridinyl and R² is CN. 155E  Q²is 2-Cl-3-thienyl and R² is Me. 156E  Q² is 2-Cl-3-thienyl and R² is Cl.157E  Q² is 2-Cl-3-thienyl and R² is Br. 158E  Q² is 2-Cl-3-thienyl andR² is Et. 159E  Q² is 2-Cl-3-thienyl and R² is CN. 160E  Q² is2,5-di-Cl-3-thienyl and R² is Me. 161E  Q² is 2,5-di-Cl-3-thienyl and R²is Cl. 162E  Q² is 2,5-di-Cl-3-thienyl and R² is Br. 163E  Q² is2,5-di-Cl-3-thienyl and R² is Et. 164E  Q² is 2,5-di-Cl-3-thienyl and R²is CN.Formulation/Utility

A compound of this invention will generally be used as a fungicidalactive ingredient in a composition, i.e. formulation, with at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, which serves as a carrier. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions and/or suspoemulsions)and the like, which optionally can be thickened into gels. The generaltypes of aqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsionand suspo-emulsion. The general types of nonaqueous liquid compositionsare emulsifiable concentrate, microemulsifiable concentrate, dispersibleconcentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying.

Such liquid and solid formulations are formulated to be readily dilutedin the spray medium, usually water. Spray volumes can range from aboutone to several thousand liters per hectare, but more typically are inthe range from about ten to several hundred liters per hectare.Sprayable formulations can be tank mixed with water or another suitablemedium for foliar treatment by aerial or ground application, or forapplication to the growing medium of the plant. Liquid and dryformulations can be metered directly into drip irrigation systems ormetered into the furrow during planting. Liquid and solid formulationscan be applied onto seeds of crops and other desirable vegetation asseed treatments before planting to protect developing roots and othersubterranean plant parts and/or foliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and PowdersOil Dispersions, Suspensions,    1-50 40-99    0-50 Emulsions, Solutions(including Emulsifiable Concentrates) Dusts    1-25 70-99    0-5 Granules and Pellets 0.001-95 5-99.999 0-15 High Strength Compositions  90-99 0-10    0-2 

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, polypropyleneglycol, propylene carbonate, butylene carbonate, paraffins (e.g., whitemineral oils, normal paraffins, isoparaffins), alkylbenzenes,alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatichydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes,ketones such as cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters and γ-butyrolactone, and alcohols, which can be linear,branched, saturated or unsaturated, such as methanol, ethanol,n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol,2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol,cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol,cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzylalcohol. Liquid diluents also include glycerol esters of saturated andunsaturated fatty acids (typically C₆-C₂₂), such as plant seed and fruitoils (e.g., oils of olive, castor, linseed, sesame, corn (maize),peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed,coconut and palm kernel), animal-sourced fats (e.g., beef tallow, porktallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquiddiluents also include alkylated fatty acids (e.g., methylated,ethylated, butylated) wherein the fatty acids may be obtained byhydrolysis of glycerol esters from plant and animal sources, and can bepurified by distillation. Typical liquid diluents are described inMarsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 or Formula 1A and any other active ingredientsare typically incorporated into the present compositions by dissolvingthe active ingredient in a solvent or by grinding in a liquid or drydiluent. Solutions, including emulsifiable concentrates, can be preparedby simply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 μmrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can beprepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Tables A-C. Without further elaboration, it isbelieved that one skilled in the art using the preceding description canutilize the present invention to its fullest extent. The followingExamples are, therefore, to be constructed as merely illustrative, andnot limiting of the disclosure in any way whatsoever. Percentages are byweight except where otherwise indicated.

Example A

High Strength Concentrate Compound 10 98.5% silica aerogel 0.5%synthetic amorphous fine silica 1.0%

Example B

Wettable Powder Compound 3 65.0% dodecylphenol polyethylene glycol ether2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0%montmorillonite (calcined) 23.0%

Example C

Granule Compound 10 10.0% attapulgite granules (low volatile matter,90.0% 0.71/0.30 mm; U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet Compound 14 25.0% anhydrous sodium sulfate 10.0% crudecalcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate Compound 3 10.0% polyoxyethylene sorbitolhexoleate 20.0% C₆-C₁₀ fatty acid methyl ester 70.0%

Example F

Microemulsion Compound 10 5.0% polyvinylpyrrolidone-vinyl acetatecopolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water20.0%

Example G

Seed Treatment Compound 14 20.00% polyvinylpyrrolidone-vinyl acetatecopolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00%polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol(POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water65.75%

Water-soluble and water-dispersible formulations are typically dilutedwith water to form aqueous compositions before application. Aqueouscompositions for direct applications to the plant or portion thereof(e.g., spray tank compositions) typically at least about 1 ppm or more(e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.

The compounds of this invention are useful as plant disease controlagents. The present invention therefore further comprises a method forcontrolling plant diseases caused by fungal plant pathogens comprisingapplying to the plant or portion thereof to be protected, or to theplant seed to be protected, an effective amount of a compound of theinvention or a fungicidal composition containing said compound. Thecompounds and/or compositions of this invention provide control ofdiseases caused by a broad spectrum of fungal plant pathogens in theBasidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They areeffective in controlling a broad spectrum of plant diseases,particularly foliar pathogens of ornamental, turf, vegetable, field,cereal, and fruit crops. These pathogens include: Oomycetes, includingPhytophthora diseases such as Phytophthora infestans, Phytophthoramegasperma, Phytophthora parasitica, Phytophthora cinnamomi andPhytophthora capsici, Pythium diseases such as Pythium aphanidermatum,and diseases in the Peronosporaceae family such as Plasmopara viticola,Peronospora spp. (including Peronospora tabacina and Peronosporaparasitica), Pseudoperonospora spp. (including Pseudoperonosporacubensis) and Bremia lactucae; Ascomycetes, including Alternariadiseases such as Alternaria solani and Alternaria brassicae, Guignardiadiseases such as Guignardia bidwell, Venturia diseases such as Venturiainaequalis, Septoria diseases such as Septoria nodorum and Septoriatritici, powdery mildew diseases such as Erysiphe spp. (includingErysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerothecafuligena and Podosphaera leucotricha, Pseudocercosporellaherpotrichoides, Botrytis diseases such as Botrytis cinerea, Moniliniafructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum,Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases suchas Helminthosporium tritici repentis, Pyrenophora teres, anthracnosediseases such as Glomerella or Colletotrichum spp. (such asColletotrichum graminicola and Colletotrichum orbiculare), andGaeumannomyces graminis; Basidiomycetes, including rust diseases causedby Puccinia spp. (such as Puccinia recondite, Puccinia striiformis,Puccinia hordei, Puccinia graminis and Puccinia arachidis), Hemileiavastatrix and Phakopsora pachyrhizi; other pathogens includingRutstroemia floccosum (also known as Sclerontina homoeocarpa);Rhizoctonia spp. (such as Rhizoctonia solani); Fusarium diseases such asFusarium roseum, Fusarium graminearum and Fusarium oxysporum;Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis;Cercosporidium personatum, Cercospora arachidicola and Cercosporabeticola; and other genera and species closely related to thesepathogens. In addition to their fungicidal activity, the compositions orcombinations also have activity against bacteria such as Erwiniaamylovora, Xanthomonas campestris, Pseudomonas syringae, and otherrelated species.

Plant disease control is ordinarily accomplished by applying aneffective amount of a compound of this invention either pre- orpost-infection, to the portion of the plant to be protected such as theroots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media(soil or sand) in which the plants to be protected are growing. Thecompounds can also be applied to seeds to protect the seeds andseedlings developing from the seeds. The compounds can also be appliedthrough irrigation water to treat plants.

Rates of application for these compounds (i.e. a fungicidally effectiveamount) can be influenced by factors such as the plant diseases to becontrolled, the plant species to be protected, ambient moisture andtemperature and should be determined under actual use conditions. Oneskilled in the art can easily determine through simple experimentationthe fungicidally effective amount necessary for the desired level ofplant disease control. Foliage can normally be protected when treated ata rate of from less than about 1 g/ha to about 5,000 g/ha of activeingredient. Seed and seedlings can normally be protected when seed istreated at a rate of from about 0.1 to about 10 g per kilogram of seed.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including fungicides,insecticides, nematocides, bactericides, acaricides, herbicides,herbicide safeners, growth regulators such as insect molting inhibitorsand rooting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, plant nutrients, otherbiologically active compounds or entomopathogenic bacteria, virus orfungi to form a multi-component pesticide giving an even broaderspectrum of agricultural protection. Thus the present invention alsopertains to a composition comprising a compound of Formula 1 or Formula1A (in a fungicidally effective amount) and at least one additionalbiologically active compound or agent (in a biologically effectiveamount) and can further comprise at least one of a surfactant, a soliddiluent or a liquid diluent. The other biologically active compounds oragents can be formulated in compositions comprising at least one of asurfactant, solid or liquid diluent. For mixtures of the presentinvention, one or more other biologically active compounds or agents canbe formulated together with a compound of Formula 1 or Formula 1A, toform a premix, or one or more other biologically active compounds oragents can be formulated separately from the compound of Formula 1 orFormula 1A, and the formulations combined together before application(e.g., in a spray tank) or, alternatively, applied in succession.

Of note is a composition which in addition to the compound of Formula 1or Formula 1A include at least one fungicidal compound selected from thegroup consisting of the classes (1) methyl benzimidazole carbamate (MBC)fungicides; (2) dicarboximide fungicides; (3) demethylation inhibitor(DMI) fungicides; (4) phenylamide fungicides; (5) amine/morpholinefungicides; (6) phospholipid biosynthesis inhibitor fungicides; (7)carboxamide fungicides; (8) hydroxy(2-amino-)pyrimidine fungicides; (9)anilinopyrimidine fungicides; (10) N-phenyl carbamate fungicides; (11)quinone outside inhibitor (QoI) fungicides; (12) phenylpyrrolefungicides; (13) quinoline fungicides; (14) lipid peroxidation inhibitorfungicides; (15) melanin biosynthesis inhibitors-reductase (MBI-R)fungicides; (16) melanin biosynthesis inhibitors-dehydratase (MBI-D)fungicides; (17) hydroxyanilide fungicides; (18) squalene-epoxidaseinhibitor fungicides; (19) polyoxin fungicides; (20) phenylureafungicides; (21) quinone inside inhibitor (QiI) fungicides; (22)benzamide fungicides; (23) enopyranuronic acid antibiotic fungicides;(24) hexopyranosyl antibiotic fungicides; (25) glucopyranosylantibiotic: protein synthesis fungicides; (26) glucopyranosylantibiotic: trehalase and inositol biosynthesis fungicides; (27)cyanoacetamideoxime fungicides; (28) carbamate fungicides; (29)oxidative phosphorylation uncoupling fungicides; (30) organo tinfungicides; (31) carboxylic acid fungicides; (32) heteroaromaticfungicides; (33) phosphonate fungicides; (34) phthalamic acidfungicides; (35) benzotriazine fungicides; (36) benzene-sulfonamidefungicides; (37) pyridazinone fungicides; (38) thiophene-carboxamidefungicides; (39) pyrimidinamide fungicides; (40) carboxylic acid amide(CAA) fungicides; (41) tetracycline antibiotic fungicides; (42)thiocarbamate fungicides; (43) benzamide fungicides; (44) host plantdefense induction fungicides; (45) multi-site contact activityfungicides; (46) fungicides other than classes (1) through (45); andsalts of compounds of classes (1) through (46).

Further descriptions of these classes of fungicidal compounds areprovided below.

(1) “Methyl benzimidazole carbamate (MBC) fungicides” (FungicideResistance Action Committee (FRAC) code 1) inhibit mitosis by binding toβ-tubulin during microtubule assembly. Inhibition of microtubuleassembly can disrupt cell division, transport within the cell and cellstructure. Methyl benzimidazole carbamate fungicides includebenzimidazole and thiophanate fungicides. The benzimidazoles includebenomyl, carbendazim, fuberidazole and thiabendazole. The thiophanatesinclude thiophanate and thiophanate-methyl.

(2) “Dicarboximide fungicides” (Fungicide Resistance Action Committee(FRAC) code 2) are proposed to inhibit a lipid peroxidation in fungithrough interference with NADH cytochrome c reductase. Examples includechlozolinate, iprodione, procymidone and vinclozo lin.

(3) “Demethylation inhibitor (DMI) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 3) inhibit C14-demethylase, which plays arole in sterol production. Sterols, such as ergosterol, are needed formembrane structure and function, making them essential for thedevelopment of functional cell walls. Therefore, exposure to thesefungicides results in abnormal growth and eventually death of sensitivefungi. DMI fungicides are divided between several chemical classes:azoles (including triazoles and imidazoles), pyrimidines, piperazinesand pyridines. The triazoles include azaconazole, bitertanol,bromuconazole, cyproconazole, difenoconazole, diniconazole (includingdiniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,metconazole, myclobutanil, penconazole, propiconazole, prothioconazole,simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol,triticonazole and uniconazole. The imidazoles include clotrimazole,imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole. Thepyrimidines include fenarimol and nuarimol. The piperazines includetriforine. The pyridines include pyrifenox. Biochemical investigationshave shown that all of the above mentioned fungicides are DMI fungicidesas described by K. H. Kuck et al. in Modern SelectiveFungicides—Properties, applications and Mechanisms of Action, H. Lyr(Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

(4) “Phenylamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 4) are specific inhibitors of RNA polymerase in Oomycetefungi. Sensitive fungi exposed to these fungicides show a reducedcapacity to incorporate uridine into rRNA. Growth and development insensitive fungi is prevented by exposure to this class of fungicide.Phenylamide fungicides include acylalanine, oxazolidinone andbutyrolactone fungicides. The acylalanines include benalaxyl,benalaxyl-M, furalaxyl, metalaxyl and metalaxyl-M/mefenoxam. Theoxazolidinones include oxadixyl. The butyrolactones include ofurace.

(5) “Amine/morpholine fungicides” (Fungicide Resistance Action Committee(FRAC) code 5) inhibit two target sites within the sterol biosyntheticpathway, Δ⁸→Δ⁷ isomerase and Δ¹⁴ reductase. Sterols, such as ergosterol,are needed for membrane structure and function, making them essentialfor the development of functional cell walls. Therefore, exposure tothese fungicides results in abnormal growth and eventually death ofsensitive fungi. Amine/morpholine fungicides (also known as non-DMIsterol biosynthesis inhibitors) include morpholine, piperidine andspiroketal-amine fungicides. The morpholines include aldimorph,dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidinesinclude fenpropidin and piperalin. The spiroketal-amines includespiroxamine.

(6) “Phospholipid biosynthesis inhibitor fungicides” (FungicideResistance Action Committee (FRAC) code 6) inhibit growth of fungi byaffecting phospholipid biosynthesis. Phospholipid biosynthesisfungicides include phosphorothiolate and dithiolane fungicides. Thephosphorothiolates include edifenphos, iprobenfos and pyrazophos. Thedithiolanes include isoprothiolane.

(7) “Carboxamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 7) inhibit Complex II (succinate dehydrogenase) fungalrespiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle)named succinate dehydrogenase. Inhibiting respiration prevents thefungus from making ATP, and thus inhibits growth and reproduction.Carboxamide fungicides include benzamides, furan carboxamides, oxathiincarboxamides, thiazole carboxamides, pyrazole carboxamides and pyridinecarboxamides. The benzamides include benodanil, flutolanil and mepronil.The furan carboxamides include fenfuram. The oxathiin carboxamidesinclude carboxin and oxycarboxin. The thiazole carboxamides includethifluzamide. The pyrazole carboxamides include furametpyr,penthiopyrad, bixafen, isopyrazam,N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamideand penflufen(N-[2-(1,3-dimethyl-butyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide).The pyridine carboxamides include boscalid.

(8) “Hydroxy(2-amino-)pyrimidine fungicides” (Fungicide ResistanceAction Committee (FRAC) code 8) inhibit nucleic acid synthesis byinterfering with adenosine deaminase. Examples include bupirimate,dimethirimol and ethirimol.

(9) “Anilinopyrimidine fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 9) are proposed to inhibit biosynthesis of theamino acid methionine and to disrupt the secretion of hydrolytic enzymesthat lyse plant cells during infection. Examples include cyprodinil,mepanipyrim and pyrimethanil.

(10) “N-Phenyl carbamate fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 10) inhibit mitosis by binding to β-tubulin anddisrupting microtubule assembly. Inhibition of microtubule assembly candisrupt cell division, transport within the cell and cell structure.Examples include diethofencarb.

(11) “Quinone outside inhibitor (QoI) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 11) inhibit Complex III mitochondrialrespiration in fungi by affecting ubiquinol oxidase. Oxidation ofubiquinol is blocked at the “quinone outside” (Q_(o)) site of thecytochrome bc₁ complex, which is located in the inner mitochondrialmembrane of fungi. Inhibiting mitochondrial respiration prevents normalfungal growth and development. Quinone outside inhibitor fungicides(also known as strobilurin fungicides) include methoxyacrylate,methoxycarbamate, oximinoacetate, oximinoacetamide, oxazolidinedione,dihydrodioxazine, imidazolinone and benzylcarbamate fungicides. Themethoxyacrylates include azoxystrobin, enestroburin (SYP-Z071),picoxystrobin and pyraoxystrobin (SYP-3343). The methoxycarbamatesinclude pyraclostrobin and pyrametostrobin (SYP-4155). Theoximinoacetates include kresoxim-methyl and trifloxystrobin. Theoximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin,α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]-methyl]benzeneacetamideand2-[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]-amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide.The oxazolidinediones include famoxadone. The dihydrodioxazines includefluoxastrobin. The imidazolinones include fenamidone. Thebenzylcarbamates include pyribencarb.

(12) “Phenylpyrrole fungicides” (Fungicide Resistance Action Committee(FRAC) code 12) inhibit a MAP protein kinase associated with osmoticsignal transduction in fungi. Fenpiclonil and fludioxonil are examplesof this fungicide class.

(13) “Quinoline fungicides” (Fungicide Resistance Action Committee(FRAC) code 13) are proposed to inhibit signal transduction by affectingG-proteins in early cell signaling. They have been shown to interferewith germination and/or appressorium formation in fungi that causepowder mildew diseases. Quinoxyfen and tebufloquin are examples of thisclass of fungicide.

(14) “Lipid peroxidation inhibitor fungicides” (Fungicide ResistanceAction Committee (FRAC) code 14) are proposed to inhibit lipidperoxidation which affects membrane synthesis in fungi. Members of thisclass, such as etridiazole, may also affect other biological processessuch as respiration and melanin biosynthesis. Lipid peroxidationfungicides include aromatic carbon and 1,2,4-thiadiazole fungicides. Thearomatic carbon fungicides include biphenyl, chloroneb, dicloran,quintozene, tecnazene and tolclofos-methyl. The 1,2,4-thiadiazolefungicides include etridiazole.

(15) “Melanin biosynthesis inhibitors-reductase (MBI-R) fungicides”(Fungicide Resistance Action Committee (FRAC) code 16.1) inhibit thenaphthal reduction step in melanin biosynthesis. Melanin is required forhost plant infection by some fungi. Melanin biosynthesisinhibitors-reductase fungicides include isobenzofuranone,pyrroloquinolinone and triazolobenzothiazole fungicides. Theisobenzofuranones include fthalide. The pyrroloquinolinones includepyroquilon. The triazolobenzothiazoles include tricyclazole.

(16) “Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides”(Fungicide Resistance Action Committee (FRAC) code 16.2) inhibitscytalone dehydratase in melanin biosynthesis. Melanin in required forhost plant infection by some fungi. Melanin biosynthesisinhibitors-dehydratase fungicides include cyclopropanecarboxamide,carboxamide and propionamide fungicides. The cyclopropanecarboxamidesinclude carpropamid. The carboxamides include diclocymet. Thepropionamides include fenoxanil.

(17) “Hydroxyanilide fungicides (Fungicide Resistance Action Committee(FRAC) code 17) inhibit C4-demethylase which plays a role in sterolproduction. Examples include fenhexamid.

(18) “Squalene-epoxidase inhibitor fungicides” (Fungicide ResistanceAction Committee (FRAC) code 18) inhibit squalene-epoxidase inergosterol biosynthesis pathway. Sterols such as ergosterol are neededfor membrane structure and function, making them essential for thedevelopment of functional cell walls. Therefore exposure to thesefungicides results in abnormal growth and eventually death of sensitivefungi. Squalene-epoxidase inhibitor fungicides include thiocarbamate andallylamine fungicides. The thiocarbamates include pyributicarb. Theallylamines include naftifine and terbinafine.

(19) “Polyoxin fungicides” (Fungicide Resistance Action Committee (FRAC)code 19) inhibit chitin synthase. Examples include polyoxin.

(20) “Phenylurea fungicides” (Fungicide Resistance Action Committee(FRAC) code 20) are proposed to affect cell division. Examples includepencycuron.

(21) “Quinone inside inhibitor (QiI) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 21) inhibit Complex III mitochondrialrespiration in fungi by affecting ubiquinol reductase. Reduction ofubiquinol is blocked at the “quinone inside” (Q_(i)) site of thecytochrome bc₁ complex, which is located in the inner mitochondrialmembrane of fungi. Inhibiting mitochondrial respiration prevents normalfungal growth and development. Quinone inside inhibitor fungicidesinclude cyanoimidazole and sulfamoyltriazole fungicides. Thecyanoimidazoles include cyazofamid. The sulfamoyltriazoles includeamisulbrom.

(22) “Benzamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 22) inhibit mitosis by binding to β-tubulin and disruptingmicrotubule assembly Inhibition of microtubule assembly can disrupt celldivision, transport within the cell and cell structure. Examples includezoxamide.

(23) “Enopyranuronic acid antibiotic fungicides” (Fungicide ResistanceAction Committee (FRAC) code 23) inhibit growth of fungi by affectingprotein biosynthesis. Examples include blasticidin-S.

(24) “Hexopyranosyl antibiotic fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 24) inhibit growth of fungi by affecting proteinbiosynthesis. Examples include kasugamycin.

(25) “Glucopyranosyl antibiotic: protein synthesis fungicides”(Fungicide Resistance Action Committee (FRAC) code 25) inhibit growth offungi by affecting protein biosynthesis. Examples include streptomycin.

(26) “Glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides” (Fungicide Resistance Action Committee (FRAC) code 26)inhibit trehalase in inositol biosynthesis pathway. Examples includevalidamycin.

(27) “Cyanoacetamideoxime fungicides (Fungicide Resistance ActionCommittee (FRAC) code 27) include cymoxanil.

(28) “Carbamate fungicides” (Fungicide Resistance Action Committee(FRAC) code 28) are considered multi-site inhibitors of fungal growth.They are proposed to interfere with the synthesis of fatty acids in cellmembranes, which then disrupts cell membrane permeability. Propamacarb,propamacarb-hydrochloride, iodocarb, and prothiocarb are examples ofthis fungicide class.

(29) “Oxidative phosphorylation uncoupling fungicides” (FungicideResistance Action Committee (FRAC) code 29) inhibit fungal respirationby uncoupling oxidative phosphorylation. Inhibiting respiration preventsnormal fungal growth and development. This class includes2,6-dinitroanilines such as fluazinam, pyrimidonehydrazones such asferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocapand binapacryl.

(30) “Organo tin fungicides” (Fungicide Resistance Action Committee(FRAC) code 30) inhibit adenosine triphosphate (ATP) synthase inoxidative phosphorylation pathway. Examples include fentin acetate,fentin chloride and fentin hydroxide.

(31) “Carboxylic acid fungicides” (Fungicide Resistance Action Committee(FRAC) code 31) inhibit growth of fungi by affecting deoxyribonucleicacid (DNA) topoisomerase type II (gyrase). Examples include oxolinicacid.

(32) “Heteroaromatic fungicides” (Fungicide Resistance Action Committee(FRAC) code 32) are proposed to affect DNA/ribonucleic acid (RNA)synthesis. Heteroaromatic fungicides include isoxazole and isothiazolonefungicides. The isoxazoles include hymexazole and the isothiazolonesinclude octhilinone.

(33) “Phosphonate fungicides” (Fungicide Resistance Action Committee(FRAC) code 33) include phosphorous acid and its various salts,including fosetyl-aluminum.

(34) “Phthalamic acid fungicides” (Fungicide Resistance Action Committee(FRAC) code 34) include teclofthalam.

(35) “Benzotriazine fungicides” (Fungicide Resistance Action Committee(FRAC) code 35) include triazoxide.

(36) “Benzene-sulfonamide fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 36) include flusulfamide.

(37) “Pyridazinone fungicides” (Fungicide Resistance Action Committee(FRAC) code 37) include diclomezine.

(38) “Thiophene-carboxamide fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 38) are proposed to affect ATP production.Examples include silthiofam.

(39) “Pyrimidinamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 39) inhibit growth of fungi by affecting phospholipidbiosynthesis and include diflumetorim.

(40) “Carboxylic acid amide (CAA) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 40) are proposed to inhibit phospholipidbiosynthesis and cell wall deposition. Inhibition of these processesprevents growth and leads to death of the target fungus. Carboxylic acidamide fungicides include cinnamic acid amide, valinamide carbamate andmandelic acid amide fungicides. The cinnamic acid amides includedimethomorph and flumorph. The valinamide carbamates includebenthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalateand valiphenal. The mandelic acid amides include mandipropamid,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamideandN-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

(41) “Tetracycline antibiotic fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 41) inhibit growth of fungi by affecting complex 1nicotinamide adenine dinucleotide (NADH) oxidoreductase. Examplesinclude oxytetracycline.

(42) “Thiocarbamate fungicides” (Fungicide Resistance Action Committee(FRAC) code 42) include methasulfocarb.

(43) “Benzamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 43) inhibit growth of fungi by delocalization ofspectrin-like proteins. Examples include acylpicolide fungicides such asfluopicolide and fluopyram.

(44) “Host plant defense induction fungicides” (Fungicide ResistanceAction Committee (FRAC) code P) induce host plant defense mechanisms.Host plant defense induction fungicides include benzo-thiadiazole,benzisothiazole and thiadiazole-carboxamide fungicides. Thebenzo-thiadiazoles include acibenzolar-5-methyl. The benzisothiazolesinclude probenazole. The thiadiazole-carboxamides include tiadinil andisotianil.

(45) “Multi-site contact fungicides” inhibit fungal growth throughmultiple sites of action and have contact/preventive activity. Thisclass of fungicides includes: (45.1) “copper fungicides” (FungicideResistance Action Committee (FRAC) code M1)”, (45.2) “sulfur fungicides”(Fungicide Resistance Action Committee (FRAC) code M2), (45.3)“dithiocarbamate fungicides” (Fungicide Resistance Action Committee(FRAC) code M3), (45.4) “phthalimide fungicides” (Fungicide ResistanceAction Committee (FRAC) code M4), (45.5) “chloronitrile fungicides”(Fungicide Resistance Action Committee (FRAC) code M5), (45.6)“sulfamide fungicides” (Fungicide Resistance Action Committee (FRAC)code M6), (45.7) “guanidine fungicides” (Fungicide Resistance ActionCommittee (FRAC) code M7), (45.8) “triazine fungicides” (FungicideResistance Action Committee (FRAC) code M8) and (45.9) “quinonefungicides” (Fungicide Resistance Action Committee (FRAC) code M9).“Copper fungicides” are inorganic compounds containing copper, typicallyin the copper(II) oxidation state; examples include copper oxychloride,copper sulfate and copper hydroxide, including compositions such asBordeaux mixture (tribasic copper sulfate). “Sulfur fungicides” areinorganic chemicals containing rings or chains of sulfur atoms; examplesinclude elemental sulfur. “Dithiocarbamate fungicides” contain adithiocarbamate molecular moiety; examples include mancozeb, metiram,propineb, ferbam, maneb, thiram, zineb and ziram. “Phthalimidefungicides” contain a phthalimide molecular moiety; examples includefolpet, captan and captafol. “Chloronitrile fungicides” contain anaromatic ring substituted with chloro and cyano; examples includechlorothalonil. “Sulfamide fungicides” include dichlofluanid andtolyfluanid. “Guanidine fungicides” include dodine, guazatine,iminoctadine albesilate and iminoctadine triacetate. “Triazinefungicides” include anilazine. “Quinone fungicides” include dithianon.

(46) “Fungicides other than fungicides of classes (1) through (45)”include certain fungicides whose mode of action may be unknown. Theseinclude: (46.1) “thiazole carboxamide fungicides” (Fungicide ResistanceAction Committee (FRAC) code U5), (46.2) “phenyl-acetamide fungicides”(Fungicide Resistance Action Committee (FRAC) code U6), (46.3)“quinazolinone fungicides” (Fungicide Resistance Action Committee (FRAC)code U7), (46.4) “benzophenone fungicides” (Fungicide Resistance ActionCommittee (FRAC) code U8) and (46.5) “triazolopyrimidine fungicides”.The thiazole carboxamides include ethaboxam. The phenyl-acetamidesinclude cyflufenamid andN-[[(cyclopropylmethoxy)-amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide.The quinazolinones include proquinazid. The benzophenones includemetrafenone. The triazolopyrimidines include ametoctradin. Class (46)(i.e. “Fungicides other than classes (1) through (45)”) also includesbethoxazin, fluxapyroxad, neo-asozin (ferric methanearsonate),pyriofenone, pyrroInitrin, quinomethionate, tebufloquin,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide,2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile,3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine,4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]-propyl]carbamate,5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-1-yl)[1,2,4]-triazolo[1,5-a]pyrimidine,N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]-benzeneacetamide,N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,1-[(2-propenylthio)carbonyl]-2-(1-methylethyl)-4-(2-methylphenyl)-5-amino-1H-pyrazol-3-one,N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,3-(di-fluoromethyl)-N-[9-(difluoromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-1H-pyrazole-4-carboxamide,N-[9-(dibromomethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,N-[9-(dibromomethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,N-[9-(difluoromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamideandN-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methyl-methanimidamide.

Therefore of note is a mixture (i.e. composition) comprising a compoundof Formula 1 or Formula 1A and at least one fungicidal compound selectedfrom the group consisting of the aforedescribed classes (1) through(46). Also of note is a composition comprising said mixture (infungicidally effective amount) and further comprising at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents. Of particular note is a mixture(i.e. composition) comprising a compound of Formula 1 or Formula 1A andat least one fungicidal compound selected from the group of specificcompounds listed above in connection with classes (1) through (46). Alsoof particular note is a composition comprising said mixture (infungicidally effective amount) and further comprising at least oneadditional surfactant selected from the group consisting of surfactants,solid diluents and liquid diluents.

Examples of other biologically active compounds or agents with whichcompounds of this invention can be formulated are: insecticides such asabamectin, acephate, acetamiprid, acrinathrin, amidoflumet (S-1955),avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate,buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin,dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin,fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate,tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos,halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb,isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone,metaldehyde, methamidophos, methidathion, methomyl, methoprene,methoxychlor, methoxyfenozide, metofluthrin, milbemycin oxime,monocrotophos, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron(XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate,phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin,pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon,pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulfoxaflor,sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon and triflumuron; and biological agents includingentomopathogenic bacteria, such as Bacillus thuringiensis subsp.aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulateddelta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII);entomopathogenic fungi, such as green muscardine fungus; andentomopathogenic virus including baculovirus, nucleopolyhedro virus(NPV) such as HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). The effect ofthe exogenously applied fungicidal compounds of this invention may besynergistic with the expressed toxin proteins.

General references for agricultural protectants (i.e. insecticides,fungicides, nematocides, acaricides, herbicides and biological agents)include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed.,British Crop Protection Council, Farnham, Surrey, U.K., 2003 and TheBioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British CropProtection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 or Formula 1A is typically between about1:3000 and about 3000:1. Of note are weight ratios between about 1:300and about 300:1 (for example ratios between about 1:30 and about 30:1).One skilled in the art can easily determine through simpleexperimentation the biologically effective amounts of active ingredientsnecessary for the desired spectrum of biological activity. It will beevident that including these additional components may expand thespectrum of diseases controlled beyond the spectrum controlled by thecompound of Formula 1 or Formula 1A alone.

In certain instances, combinations of a compound of this invention withother biologically active (particularly fungicidal) compounds or agents(i.e. active ingredients) can result in a greater-than-additive (i.e.synergistic) effect. Reducing the quantity of active ingredientsreleased in the environment while ensuring effective pest control isalways desirable. When synergism of fungicidal active ingredients occursat application rates giving agronomically satisfactory levels of fungalcontrol, such combinations can be advantageous for reducing cropproduction cost and decreasing environmental load.

Of note is a combination of a compound of Formula 1 or Formula 1A withat least one other fungicidal active ingredient. Of particular note issuch a combination where the other fungicidal active ingredient hasdifferent site of action from the compound of Formula 1 or Formula 1A.In certain instances, a combination with at least one other fungicidalactive ingredient having a similar spectrum of control but a differentsite of action will be particularly advantageous for resistancemanagement. Thus, a composition of the present invention can furthercomprise a biologically effective amount of at least one additionalfungicidal active ingredient having a similar spectrum of control but adifferent site of action.

Of particular note are compositions which in addition to compound ofFormula 1 or Formula 1A include at least one compound selected from thegroup consisting of (1) alkylenebis(dithiocarbamate) fungicides; (2)cymoxanil; (3) phenylamide fungicides; (4) proquinazid(6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone); (5) chlorothalonil;(6) carboxamides acting at complex II of the fungal mitochondrialrespiratory electron transfer site; (7) quinoxyfen; (8) metrafenone; (9)cyflufenamid; (10) cyprodinil; (11) copper compounds; (12) phthalimidefungicides; (13) fosetyl-aluminum; (14) benzimidazole fungicides; (15)cyazofamid; (16) fluazinam; (17) iprovalicarb; (18) propamocarb; (19)validomycin; (20) dichlorophenyl dicarboximide fungicides; (21)zoxamide; (22) fluopicolide; (23) mandipropamid; (24) carboxylic acidamides acting on phospholipid biosynthesis and cell wall deposition;(25) dimethomorph; (26) non-DMI sterol biosynthesis inhibitors; (27)inhibitors of demethylase in sterol biosynthesis; (28) bc₁ complexfungicides; and salts of compounds of (1) through (28).

Further descriptions of classes of fungicidal compounds are providedbelow.

Sterol biosynthesis inhibitors (group (27)) control fungi by inhibitingenzymes in the sterol biosynthesis pathway. Demethylase-inhibitingfungicides have a common site of action within the fungal sterolbiosynthesis pathway, involving inhibition of demethylation at position14 of lanosterol or 24-methylene dihydrolanosterol, which are precursorsto sterols in fungi. Compounds acting at this site are often referred toas demethylase inhibitors, DMI fungicides, or DMIs. The demethylaseenzyme is sometimes referred to by other names in the biochemicalliterature, including cytochrome P-450 (14DM). The demethylase enzyme isdescribed in, for example, J. Biol. Chem. 1992, 267, 13175-79 andreferences cited therein. DMI fungicides are divided between severalchemical classes: azoles (including triazoles and imidazoles),pyrimidines, piperazines and pyridines. The triazoles includeazaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole(including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,prothioconazole, quinconazole, simeconazole, tebuconazole,tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.The imidazoles include clotrimazole, econazole, imazalil, isoconazole,miconazole, oxpoconazole, prochloraz and triflumizole. The pyrimidinesinclude fenarimol, nuarimol and triarimol. The piperazines includetriforine. The pyridines include buthiobate and pyrifenox. Biochemicalinvestigations have shown that all of the above mentioned fungicides areDMI fungicides as described by K. H. Kuck et al. in Modern SelectiveFungicides—Properties, Applications and Mechanisms of Action, H. Lyr(Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

bc₁ Complex Fungicides (group 28) have a fungicidal mode of action whichinhibits the bc₁ complex in the mitochondrial respiration chain. The bc₁complex is sometimes referred to by other names in the biochemicalliterature, including complex III of the electron transfer chain, andubihydroquinone:cytochrome c oxidoreductase. This complex is uniquelyidentified by Enzyme Commission number EC1.10.2.2. The bc₁ complex isdescribed in, for example, J. Biol. Chem. 1989, 264, 14543-48; MethodsEnzymol. 1986, 126, 253-71; and references cited therein. Strobilurinfungicides such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071),fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin andtrifloxystrobin are known to have this mode of action (H. Sauter et al.,Angew. Chem. Int. Ed. 1999, 38, 1328-1349). Other fungicidal compoundsthat inhibit the bc₁ complex in the mitochondrial respiration chaininclude famoxadone and fenamidone.

Alkylenebis(dithiocarbamate)s (group (1)) include compounds such asmancozeb, maneb, propineb and zineb. Phenylamides (group (3)) includecompounds such as metalaxyl, benalaxyl, furalaxyl and oxadixyl.Carboxamides (group (6)) include compounds such as boscalid, carboxin,fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, thifluzamide,penthiopyrad andN-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide(PCT Patent Publication WO 2003/010149), and are known to inhibitmitochondrial function by disrupting complex II (succinatedehydrogenase) in the respiratory electron transport chain. Coppercompounds (group (11)) include compounds such as copper oxychloride,copper sulfate and copper hydroxide, including compositions such asBordeaux mixture (tribasic copper sulfate). Phthalimides (group (12))include compounds such as folpet and captan. Benzimidazole fungicides(group (14)) include benomyl and carbendazim. Dichlorophenyldicarboximide fungicides (group (20)) include chlozolinate,dichlozoline, iprodione, isovaledione, myclozolin, procymidone andvinclozolin.

Non-DMI sterol biosynthesis inhibitors (group (26)) include morpholineand piperidine fungicides. The morpholines and piperidines are sterolbiosynthesis inhibitors that have been shown to inhibit steps in thesterol biosynthesis pathway at a point later than the inhibitionsachieved by the DMI sterol biosynthesis (group (27)). The morpholinesinclude aldimorph, dodemorph, fenpropimorph, tridemorph andtrimorphamide. The piperidines include fenpropidin.

Of further note are combinations of compounds of Formula 1 or Formula 1Awith azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin,picoxystrobin, dimoxystrobin, metominostrobin/fenominostrobin,carbendazim, chlorothalonil, quinoxyfen, metrafenone, cyflufenamid,fenpropidine, fenpropimorph, bromuconazole, cyproconazole,difenoconazole, epoxiconazole, fenbuconazole, flusilazole, hexaconazole,ipconazole, metconazole, penconazole, propiconazole, proquinazid,prothioconazole, tebuconazole, triticonazole, famoxadone, prochloraz,penthiopyrad and boscalid (nicobifen).

Specifically preferred mixtures (compound numbers refer to compounds inIndex Tables A-C below) are selected from the group: combinations ofCompound 3, Compound 10, Compound 12, Compound 14, Compound 17, Compound18, Compound 19, Compound 21, Compound 30, Compound 31, Compound 33,Compound 36, Compound 37, Compound 40, Compound 42, Compound 45,Compound 61, Compound 69, Compound 80, Compound 82, Compound 85,Compound 90, Compound 97, Compound 112, Compound 119, Compound 120,Compound 126, Compound 137, Compound 142, Compound 157, Compound 160, orCompound 179 with azoxystrobin, combinations of Compound 3, Compound 10,Compound 12, Compound 14, Compound 17, Compound 18, Compound 19,Compound 21, Compound 30, Compound 31, Compound 33, Compound 36,Compound 37, Compound 40, Compound 42, Compound 45, Compound 61,Compound 69, Compound 80, Compound 82, Compound 85, Compound 90,Compound 97, Compound 112, Compound 119, Compound 120, Compound 126,Compound 137, Compound 142, Compound 157, Compound 160, or Compound 179with kresoxim-methyl, combinations of Compound 3, Compound 10, Compound12, Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withtrifloxystrobin, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withpicoxystrobin, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withmetominostrobin/fenominostrobin, combinations of Compound 3, Compound10, Compound 12, Compound 14, Compound 17, Compound 18, Compound 19,Compound 21, Compound 30, Compound 31, Compound 33, Compound 36,Compound 37, Compound 40, Compound 42, Compound 45, Compound 61,Compound 69, Compound 80, Compound 82, Compound 85, Compound 90,Compound 97, Compound 112, Compound 119, Compound 120, Compound 126,Compound 137, Compound 142, Compound 157, Compound 160, or Compound 179with quinoxyfen, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withmetrafenone, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withfenpropidine, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withfenpropimorph, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withcyproconazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withepoxiconazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withflusilazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withmetconazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withpropiconazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withproquinazid, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withprothioconazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withtebuconazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withtriticonazole, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withfamoxadone, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 withpenthiopyrad, combinations of Compound 3, Compound 10, Compound 12,Compound 14, Compound 17, Compound 18, Compound 19, Compound 21,Compound 30, Compound 31, Compound 33, Compound 36, Compound 37,Compound 40, Compound 42, Compound 45, Compound 61, Compound 69,Compound 80, Compound 82, Compound 85, Compound 90, Compound 97,Compound 112, Compound 119, Compound 120, Compound 126, Compound 137,Compound 142, Compound 157, Compound 160, or Compound 179 with3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluoro[1,1′-biphenyl]-2-yl)-1H-pyrazole-4-carboxamide,combinations of Compound 3, Compound 10, Compound 12, Compound 14,Compound 17, Compound 18, Compound 19, Compound 21, Compound 30,Compound 31, Compound 33, Compound 36, Compound 37, Compound 40,Compound 42, Compound 45, Compound 61, Compound 69, Compound 80,Compound 82, Compound 85, Compound 90, Compound 97, Compound 112,Compound 119, Compound 120, Compound 126, Compound 137, Compound 142,Compound 157, Compound 160, or Compound 179 with5-ethyl-6-octyl-[1,2,4]triazole[1,5-a]pyrimidin-7-amine, andcombinations of Compound 3, Compound 10, Compound 12, Compound 14,Compound 17, Compound 18, Compound 19, Compound 21, Compound 30,Compound 31, Compound 33, Compound 36, Compound 37, Compound 40,Compound 42, Compound 45, Compound 61, Compound 69, Compound 80,Compound 82, Compound 85, Compound 90, Compound 97, Compound 112,Compound 119, Compound 120, Compound 126, Compound 137, Compound 142,Compound 157, Compound 160, or Compound 179 with Initium®.

The control efficacy of compounds of this invention on specificpathogens is demonstrated below in TABLE A. The pathogen controlprotection afforded by the compounds is not limited, however, to thesespecies (i.e. species described in Tests A-F below). Descriptions of thecompounds are provided in Index Tables A-C below. The followingabbreviations are used in the index tables: Me is methyl, MeO ismethoxy, EtO is ethoxy, CN is cyano, NO₂ is nitro and Ph is phenyl. Theabbreviation “Cmpd. No.” means compound number, and “Ex.” stands for“Example” and is followed by a number indicating in which example thecompound is prepared. Mass spectra (MS) are reported as the molecularweight of the highest isotopic abundance parent ion (M+1) formed byaddition of H⁺ (molecular weight of 1) to the molecule, observed by massspectrometry using atmospheric pressure chemical ionization (AP⁺).

INDEX TABLE A

Cmpd. No. R² Q¹ Q² m.p. (° C.) AP+ (M + 1)  3 Me 2-Cl, 4-F—Ph 2-Cl,6-F—Ph 383  9 Cl 2,4-di-F—Ph 2-Cl, 4-F—Ph 104-107  10 Me 2-Cl, 4-F—Ph2,6-di-F—Ph 142-144 14 (Ex. 4) Me 2,4-di-F—Ph 2,6-di-F—Ph ** **  15 Me2,4,6-tri-F—Ph 2,6-di-F—Ph 369  16 Me 2,6-di-F, 4-MeO—Ph 2,6-di-F—Ph 381 17 Me 2,4-di-F—Ph 2-Cl, 4-F—Ph 367  18 Me 2-Cl, 4-F—Ph 2-Cl, 4-F—Ph 383 19 Me 2,4,6-tri-F—Ph 2-Cl, 4-F—Ph 385  20 Me 2,6-di-F, 4-MeO—Ph 2-Cl,4-F—Ph 397  21 Me 2-Br, 4-F—Ph 2,6-di-F—Ph 411  22 Me 2-F, 4-CN—Ph2,6-diF—Ph * *  23 Me 2-Br, 4-F—Ph 2-Cl, 4-F—Ph 429  25 Me 2-F, 4-CN—Ph2-Cl, 4-F—Ph 374 30 (Ex. 9) Br 2,4-di-F—Ph 2-Cl, 4-F—Ph ** **  33 Me2,4-di-F—Ph 2-Cl, 6-F—Ph 367  34 Me 2,4,6-tri-F—Ph 2-Cl, 6-F—Ph 385  37Me 2-Br, 4-F—Ph 2-Cl, 6-F—Ph 427  38 Me 4-CN, 2-F—Ph 2-Cl, 6-F—Ph 374 39 Me 2,6-di-F, 4-MeO—Ph 2-Cl, 6-F—Ph 397 53 (Ex. 11) CN 2-Cl, 4-F—Ph2,6-di-F—Ph ** **  55 Me 2,4,6-tri-Cl—Ph 2-Cl, 6-F—Ph 435  61 Me 2-Cl,4-F—Ph 2,4,6-tri-F—Ph 385  66 Me 2,4-di-F—Ph 2,4,6-tri-F—Ph 369  69 Me2-Cl, 4-F—Ph 2,6-di-Cl—Ph 160-162  70 Me 2,4,6-tri-F—Ph 2,6-di-Cl—Ph137-139  71 Me 2-Cl, 4-F—Ph 2,4-di-F—Ph * * 72 (Ex. 8) Me 2,4-di-F—Ph2,4-di-F—Ph ** **  74 Me 2,4-di-F—Ph 2,6-di-Cl—Ph 125-128  76 Me2,4-di-F—Ph 2-Br, 4-F—Ph 411  77 Me 4-Cl—Ph 2,6-di-Cl—Ph 383 79 Note 1Me 2-Cl, 4-F—Ph 2-Br 411 80 Note 2 Me 2-Cl, 4-F—Ph 2-Br 411  82 Me2,4,6-tri-F—Ph 2-Br, 4-F—Ph * *  85 Me 2,6-di-Cl—Ph 2-Cl, 6-F—Ph 399 86Note 3 Me 2-Cl, 4-F—Ph 2,6-di-F—Ph 61-71 87 Note 4 Me 2-Cl, 4-F—Ph2,6-di-F—Ph 367  88 Me 2-Br, 4-F—Ph 2-I 503  90 Me 2,4-di-Cl—Ph 2-Cl,6-F—Ph 401  94 Me 2-Cl, 4-F—Ph 2-Br, 6-F—Ph 429  95 Me 2-Cl, 4-F—Ph2-Br, 4-F—Ph * *  97 Me 2,4-di-F—Ph 2,4-di-Cl—Ph 123-127  98 Me 2-Cl,4-F—Ph 3,5-di-Cl-4-pyridinyl 400  99 Me 2-I, 4-F—Ph 2-Cl, 4-F—Ph 475 100Me 2-Cl, 4-F—Ph 2,4-di-Cl—Ph 401 101 Me 4-Cl, 2-F—Ph 2,4-di-Cl—Ph150-152 103 Note 3 Me 2-Cl, 4-F—Ph 4-F, 2-I—Ph 148-151 104 Note 4 Me2-Cl, 4-F—Ph 4-F, 2-I—Ph 475 105 Me 2-Cl, 4-F—Ph 4-F—Ph 349 106 Me2,4-di-F—Ph 4-Br-2,6-di-4-F—Ph 431 112 Me 2,4-di-F—Ph 4-CN-2,6-di-4-F—Ph170-173 113 Br 2-Br, 4-F—Ph 2,6-di-4-F—Ph 118-120 114 Br 2,4,6-tri-F—Ph2,6-di-4-F—Ph 168-170 117 Cl 2,4-di-F—Ph 2,6-di-4-F—Ph 97-99 118 MeO2-Cl, 4-F—Ph 2-Cl, 4-F—Ph 399 119 Br 2-Cl, 4-F—Ph 2,6-di-4-F—Ph 83-86120 MeO 2-Cl, 4-F—Ph 2-Cl, 6-F—Ph 399 124 Br 2,4-di-F—Ph 2,6-di-F—Ph80-82 125 Br 2-Cl, 4-F—Ph 2-Cl, 4-F—Ph 142-144 126 MeO 2-Cl, 4-F—Ph2,6-di-F—Ph 383 127 EtO 2-Cl, 4-F—Ph 2,6-di-F—Ph 397 128 F₂CHO 2-Cl,4-F—Ph 2,6-di-F—Ph 419 129 Me 2-Me, 4-F—Ph 2,6-di-F—Ph 347 130 H 2-Cl,4-F—Ph 2,6-di-F—Ph 136-138 131 Br 2,4-di-F—Ph 2-Cl, 6-F—Ph 143-146 132Br 2-Br, 4-F—Ph 2-Cl, 6-F—Ph 122-125 133 Cl 2,4-di-F—Ph 2-Cl, 6-F—Ph157-160 134 Cl 2-Br, 4-F—Ph 2-Cl, 6-F—Ph 117-120 135 Cl 2-Cl, 4-F—Ph2-Cl, 6-F—Ph 131-134 136 Cl 2-Br, 4-F—Ph 2,6-di-F—Ph 100-102 137 Cl2-Cl, 4-F—Ph 2,6-di-F—Ph 113-115 138 MeO 2,3,6-tri-F—Ph 2,6-di-F—Ph 385139 MeO 2-Cl, 3,6-di-F—Ph 2,6-di-F—Ph 400 140 MeO 2-Me, 4-F—Ph 2-Cl,6-F—Ph 379 141 MeO 2-Cl, 4-F—Ph 2-Cl, 4,6-di-F—Ph 417 142 MeO 2-Cl,4-MeO—Ph 2-Cl, 6-F—Ph 411 143 MeO 2-F, 4-MeO—Ph 2-Cl, 6-F—Ph 395 144 MeO2-Cl, 3,6-di-F—Ph 2-Cl, 6-F—Ph 417 145 MeO 2,3,6-tri-F—Ph 2-Cl, 6-F—Ph401 146 Me 2,4-di-F—Ph 2-Me-1H-imidazol-1-yl 180-183 147 Me 2-Me, 4-F—Ph2-Me-1H-imidazol-1-yl 315 148 Br 2-Cl, 4-F—Ph 2-Cl, 6-F—Ph 131-134 149Br 2-Me, 4-F—Ph 2-Cl, 6-F—Ph 133-136 150 Me 2-Me, 4-F—Ph2-Cl-1H-imidazol-1-yl 165-168 151 Me 2,4-di-F—Ph 2-Cl-1H-imidazol-1-yl183-186 152 MeO 2-Cl, 4-F—Ph 2,4,6-F—Ph 401 153 MeO 2,4-di-F—Ph2,4,6-tri-F—Ph 385 154 MeO 2-F—Ph 2,4,6-tri-F—Ph 365 155 MeO 2-Cl,6-F—Ph 2,4,6-tri-F—Ph 401 156 MeO 2,4-di-F—Ph 2,6-di-F—Ph 367 157 (Ex.12) MeO 2-Me, 4-F—Ph 2,6-di-F—Ph ** ** 158 Me 2-Me 4-F—Ph3,5-di-Me-1H-pyrazol-1-yl 97-99 159 Me 2,4-di-F—Ph3,5-di-Me-1H-pyrazol-1-yl 136-138 160 MeO 2-Cl, 4-MeO—Ph 2,6-di-F—Ph 365161 MeO 2-F, 4-MeO—Ph 2,6-di-F—Ph 379 162 MeO 2-Cl, 4-F—Ph 4-Cl,2,6-di-F—Ph 417 163 Br 2,4-di-Cl—Ph 2,6-di-F—Ph 174-176 164 Br 2-Br,4-F—Ph 2-Cl, 4-F—Ph 148-150 165 Br 2-Me, 4-F—Ph 2,6-di-F—Ph 85-87 166 Me2-Cl, 4-F—Ph 3,5-di-F-4-pyridinyl * * 167 Me 2,4-di-F—Ph3,5-di-Cl-4-pyridinyl * * 168 Me 2,4-di-F—Ph 3,5-di-F-4-pyridinyl 352169 Me 2-Cl, 4-MeO—Ph 2-Cl, 4-F—Ph 395 170 Me 2-Cl, 4-MeO—Ph 2-Cl,6-F—Ph 395 171 Me 2-Cl, 4-F—Ph 2,6-di-F, 4-MeO—Ph 397 172 Me 2,4-di-F—Ph2,6-di-F, 4-MeO—Ph 381 173 Me 2,4,6-tri-F—Ph 2,6-di-F, 4-MeO—Ph 399 *SeeIndex Table D for ¹H NMR data. **See synthesis example for ¹H NMR. Note1: 99% enantiomer A. Note 2: 13% enantiomer A, 87% enantiomer B. Note 3:enantiomer A. Note 4: enantiomer B.

INDEX TABLE B

Cmpd. No. R¹ Q¹ Q² R⁴ R⁵ AP+ (M + 1)  29 Me 2,4-di-F—Ph 2-Cl, 6-F—Ph OHMe 381  54 Me 2-Cl, 4-F—Ph 2,6-di-F—Ph F H 369  67 Me 2-Cl, 4-F—Ph 2-Cl,6-F—Ph MeO H 397 68 (Ex. 5) Me 2,4-di-F—Ph 2,6-di-F—Ph F H **  75 Me2,4,6-tri-F—Ph 2-Cl, 6-F—Ph F H 387  84 Me 2-Cl, 4-F—Ph 2,6-di-F—Ph Cl H383  92 Me 2,4-di-Cl—Ph 2,6-di-F—Ph F H 384 107 Me 2-Cl, 4-F—Ph2,6-di-4-F—Ph N≡CCH₂O H 406 108 Me 2-Cl, 4-F—Ph 2,6-di-4-F—Ph CH₃C(═O)OH 409 109 Me 2-Cl, 4-F—Ph 2,6-di-4-F—Ph CH₂═CHCH₂O H 407 110 Me 2-Cl,4-F—Ph 2,6-di-4-F—Ph CH₃OCH₂O H 411 111 Me 2-Cl, 4-F 2,6-di-4-F—Ph N≡CSH 408 115 Me 2,4-di-F—Ph 2,6-di-4-F—Ph N≡CS H 392 116 Me 2,4,6-tri-F—Ph2,6-di-4-F—Ph N≡CS H 410 121 Me 2-Cl, 4-F—Ph 2-Cl, 6-F—Ph N≡CS H 424 122Me 2,4-di-F—Ph 2-Cl, 6-F—Ph N≡CS H 408 123 Me 2,4,6-tri-F—Ph 2-Cl,6-F—Ph N≡CS H 426 **See synthesis example for ¹H NMR.

INDEX TABLE C

Cmpd. No. R² Q¹ Q² X m.p. (° C.) AP+ (M + 1)  1 Me 4-F—Ph 2,4-di-F—Ph O39-40  2 Me 4-F—Ph 2-Cl, 4-F—Ph O 71-73  4 Me 2-Cl, 4-F—Ph 2-Cl, 4-F—PhO 369 5 (Ex. 3) Me 2-Cl, 4-F—Ph 2,4-di-F—Ph O ** **  6 Me 4-CN, 2-F—Ph2-Cl, 4-F—Ph O 126-128  7 Me 4-CN, 2-F—Ph 2,4-di-F—Ph O 131-133  8 Me2-Cl, 4-F—Ph 2-F, 4-CN—Ph O 139-141  11 Me 2,4-di-F—Ph 2-Cl, 4-F—Ph O353  12 Me 2,4-di-F—Ph 2-Cl, 4-MeO—Ph O 356  13 Me 2,4-di-F—Ph2,4-di-F—Ph O 62-64  24 Me 2,4-di-F—Ph 2,6-di-F—Ph C(═O) 349  26 Me2,4-di-F—Ph 2-F, 4-CN—Ph O 125-127  27 Me 2,4-di-Cl—Ph 2-Cl, 6-F—PhC(═O) 399  28 Me 2,4-di-F—Ph 2-Cl, 6-F—Ph C(═O) 365  31 Me 2-Cl, 4-F—Ph2-Cl, 4-MeO—Ph O 381 32 (Ex. 7) Me 2,4-di-F—Ph 2,4-di-F—Ph C(═O) ** ** 35 Me 2-Cl, 4-CN—Ph 2,4-di-F—Ph O 132-134  36 Me 2-Cl, 4-F—Ph 2-Cl,4-CN—Ph O 123-125 40 (Ex. 1) Me 4-CN, 2,6-di-F—Ph 2-Cl, 4-F—Ph NH ** ** 41 Me 4-F—Ph 2-Cl, 4-F—Ph NH 334  42 Me 2-Cl, 4-F—Ph 2-Cl, 4-F—Ph NH369  43 Me 2-Cl, 4-CN—Ph 2-Cl, 4-F—Ph O 133-135  44 Me 2,4-di-Cl—Ph2-Cl, 4-F—Ph NH 384 45 (Ex. 2) Me 4-Cl, 2-F—Ph 2-Cl, 4-F—Ph NH ** **  46Me 2,6-di-Cl—Ph 2-Cl, 4-F—Ph C(═O) 397  47 Me 2-Cl, 4-F—Ph 2,6-di-F—PhC(═O) 365  48 Br 2,4-di-F—Ph 2-Cl,4-F—Ph C(═O) 154-156  49 Me2,4-di-F—Ph 2-Cl, 4-F—Ph NH 352  50 Me 2-Cl, 4-F—Ph 2,6-di-F—Ph NH 352 51 Me 2,4,6-tri-Cl 2-Cl, 6-F—Ph C(═O) 433 52 (Ex. 10) CN 2-Cl, 4-F—Ph2,6-di-F—Ph C(═O) ** ** 56 (Ex. 6) Me 4-Cl—Ph 2,6-di-F—Ph S ** **  57 Me2-Cl, 4-F—Ph 2,4-di-F—Ph NH 352  58 Me 2-Br, 4-F—Ph 2-Cl, 4-F—Ph NH 412 59 Me 2-Cl, 4-F—Ph 2,4,6-tri-F—Ph C(═O) 383  60 Me 2,4-di-F—Ph2,4,6-tri-F—Ph C(═O) * *  62 Me 4-Cl—Ph 2,6-di-F—Ph S(═O)₂ 383  63 Me4-Cl—Ph 2,6-di-F—Ph S(═O) 367  64 Me 2,4-di-F—Ph 2,6-di-F—Ph NH 336  65Me 2,4-di-Cl—Ph 2,6-di-F—Ph NH 368  73 Me 2,4-di-F—Ph 2-Br, 4-F—Ph C(═O)409  78 Me 2-Cl, 4-F—Ph 2-Br—Ph C(═O) 409  81 Me 2-Br, 4-F—Ph 2-I—PhC(═O) 501  83 Me 2-Cl, 4-F—Ph 2-Br, 4-F—Ph C(═O) * *  89 Me 2,4-di-F—Ph2,4-di-Cl—Ph C(═O) 381  91 Me 2-Cl, 4-F—Ph 2,6-di-Cl—Ph N(OH) 384  93 Me2-Cl, 4-F—Ph 2-Br, 6-F—Ph C(═O) 427  96 Me 2-Cl, 4-F—Ph3,5-di-Cl-4-pyridinyl C(═O) 398 102 Me 2,4-di-F—Ph 2,6-di-F, 4-Br—PhC(═O) 429 *See Index Table D or ¹H NMR data. **See synthesis example for¹H NMR.

INDEX TABLE D Compd. No. ¹H NMR Data (CDCl₃ solution)^(a) 22 δ 7.57 (t,1H), 7.45-7.36 (m, 1H), 7.28-7.24 (m, 1H), 7.16-7.11 (m, 1H), 7.02-6.98(m, 1H), 6.86-6.82 (m, 1H), 5.88 (d, 1H), 3.60 (s, 3H), 2.26 (s, 3H),2.2 (br s, 1H). 60 δ 7.42-7.36 (m, 1H), 6.82-6.76 (m, 1H), 6.62-6.50 (m,3H), 3.69 (s, 3H), 2.46 (s, 3H). 71 δ 7.55-7.35 (m, 1H), 7.28-6.69 (m,5H), 5.78 (d, 1H), 3.51 (s, 3H), 2.16 (s, 3H), 2.2 (br s, 1H). 82 δ7.26-7.15 (m, 2H), 7.0-7.12 (m, 1H), 6.40 (m, 2H), 6.0 (d, 1H), 3.46 (s,3H), 2.38 (s, 3H), 2.42 (br s, 1H). 83 δ 7.26-7.12 (m, 3H), 6.94 (m,1H), 6.85 (dd, 1H), 6.78-6.70 (m, 1H), 3.57 (s, 3H), 2.49 (s, 3H), 2.2(br s, 1H). 95 δ 7.38-7.27 (m, 2H), 6.97-6.92 (m, 1H), 6.82-6.78 (m,1H), 6.68-6.61 (m, 2H), 5.88 (d, 1H), 3.46 (s, 3H), 2.36 (s, 3H), 2.2(br s, 1H). 166 δ 8.37-8.28 (m, 2H), 7.43 (m, 1H), 6.91 (m, 1H), 6.74(m, 1H), 5.84 (m, 1H), 3.57 (s, 3H, 2.38 (m, 1H), 2.20 (s, 3H). 167 δ8.69 (s, 1H), 8.67 (s, 1H), 7.42 (m, 1H), 6.79 (m, 1H), 6.68 (m, 1H),5.87 (m, 1H), 3.66 (s, 3H), 2.18 (s, 3H), 2.08 (m, 1H). ^(a1)HNMR dataare in ppm downfield from tetramethylsilane. Couplings are designated by(s)—singlet, (d)—doublet, (t)—triplet, (m)—multiplet, (dd)—doublet ofdoublets and (br s)—broad singlet.

BIOLOGICAL EXAMPLES OF THE INVENTION

General protocol for preparing test suspensions for Tests A-F: the testcompounds were first dissolved in acetone in an amount equal to 3% ofthe final volume and then suspended at the desired concentration (inppm) in acetone and purified water (50/50 mix by volume) containing 250ppm of the surfactant Trem® 014 (polyhydric alcohol esters). Theresulting test suspensions were then used in Tests A-F. Spraying a 200ppm test suspension to the point of run-off on the test plants was theequivalent of a rate of 800 g/ha. Unless otherwise indicated, the ratingvalues indicate a 200 ppm test suspension was used. (An asterisk “*”next to the rating value indicates a 40 ppm test suspension was used.)

Test A

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Botrytis cinerea (the causal agent of tomato Botrytis) andincubated in saturated atmosphere at 20° C. for 48 h, and then moved toa growth chamber at 24° C. for 3 days, after which time visual diseaseratings were made.

Test B

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Alternaria solani (the causal agent of tomato earlyblight) and incubated in a saturated atmosphere at 27° C. for 48 h, andthen moved to a growth chamber at 20° C. for 5 days, after which timevisual disease ratings were made.

Test C

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria nodorum (the causal agent of Septoria glumeblotch) and incubated in a saturated atmosphere at 24° C. for 48 h, andthen moved to a growth chamber at 20° C. for 6 days, after which timevisual disease ratings were made.

Test D

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria tritici (the causal agent of wheat leaf blotch)and incubated in saturated atmosphere at 24° C. for 48 h, and then movedto a growth chamber at 20° C. for 19 days, after which time visualdisease ratings were made.

Test E1

Wheat seedlings were inoculated with a spore suspension of Pucciniarecondite f. sp. tritici (the causal agent of wheat leaf rust) andincubated in a saturated atmosphere at 20° C. for 24 h, and then movedto a growth chamber at 20° C. for 2 days. After 2 days, the testsuspension was sprayed to the point of run-off on the wheat seedlings,and then the seedlings were moved back to the growth chamber at 20° C.for 6 days. Upon removal, visual disease ratings were made.

Test E2

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Puccinia recondite f. sp. tritici (the causal agent ofwheat leaf rust) and incubated in a saturated atmosphere at 20° C. for24 h, and then moved to a growth chamber at 20° C. for 7 days, afterwhich time visual disease ratings were made.

Test F

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporedust of Blumeria graminis f. sp. tritici, (also known as Erysiphegraminis f. sp. tritici, the causal agent of wheat powdery mildew) andincubated in a growth chamber at 20° C. for 8 days, after which timevisual disease ratings were made.

Results for Tests A-F are given in Table A. In the Table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls). A dash (-) indicates no testresults. An asterisk “*” next to the rating value indicates a 40 ppmtest suspension was used.

TABLE A Cmpd. Test Test Test Test Test Test Test No A B C D E1 E2 F 1100  0 0  0 38  68  91 2 100  0 0 100 77  97  99 3 100 100  100  100 99100 100 4  98  0 0 100 75  98  97 5  87  0 0  97 23  92  66 6 100 59 0100  0  99 100 7  0 96 0 100  0  9  0 8 100  0 0  99  0  40  99 9 100  00 100 100  100  99 10 100 100  99  100 98 100 100 11 100  0 0  95 91  97 96 12 100 93 0 100 65  89  98 13 100  0 0  0 66  0  72 14 100 100  99 100 96 100 100 15 100 100  86  100 68 100 100 16 100 99 0 100 54 100  9317 100 94 60  100 83 100 100 18 100 83 0 100 100  100 100 19  99 100 100  100 100  100 100 20  97*  97*  0*  100*  99*  99*  92* 21  99 100 100  100 100  100  98 22  88 84 0 100 17  88  0 23 100 67 87  100 98 100 84 24  9  0 0  0  9  79  96 25 100 99 89  100  9 100  96 26 100  0 0 — 0  79  64 27  0  0 0  0  0  0  81 28  56  0 0  0  0  8  79 29 100 64 0—  0 100  96 30 100  9 0 100 100   99  99 31 100  0 0 100  0  92  96 32 26  0 0 —  0  0  0 33 100 100  100  100 99 100 100 34 100 99 100  10084  99 100 35  98  0 0 100  9  73  0 36  96  0 0 100 18 100 100 37 10099 100  100 100 100 38  85 99 100  100  0 100  98 39  95 58 60  100 97100  99 40 100 99 99  100 91 100 100 41 100 64 0  98  0  41  0 42  99 990 100 32  99 100 43  98  0 0 100  0  98  97 44  99*  0*  0*  99*  0* 99*  100* 45  98*  33*  0*  100*  0*  95*  100* 46 — — — — — — — 47 — —— — — — — 48  26  0 0  99 —  0  0 49  100*  0*  0*  96* —  74*  87* 50 99 93 0 100  0  79  98 51 — — — — — — — 52 — — — — — — — 53  93*  99* 0*  100*  0*  93*  43* 54 100 100  99  100 100   99  99 55  99 97 78 100 99 100  95 56  0  0 0  0 60  27  97 57  99*  0*  0*  81*  0*  18* 97* 58  100*  8*  0*  100*  0*  98*  97* 59  66  0 0  58  0  80 100 60 75  0 0  0  0  55  99 61 100 100  99  100 99 100 100 62  0  0 0  0  0 28  94 63  0  0 0  0  0  28  76 64  99  0 0  48  0  55  97 65 100  0 0100  9  89 100 66 100 100  95  100 55 100  99 67  57  9 0 100 28  90 10068 100 88 99  100 100  100 100 69  99 100  96  100  0  99  97 70 — 9960  100 94 100  99 71 —  78* 73*  100*  88*  99*  99* 72 —  53*  0* 100*  18*  96*  98* 73 —  60*  0*  14*  0*   0*  34* 74 — 100  92   99 0  99  98 75 — 100* 87*  100*  74*  100*  99* 76 — 99 60  100 99 100100 77 — 93 0  99  0  79  89 78  0 31 40   0  0  79  99 79  98  0 0 10053 100  99 80  99 97 69  100 99  99  99 81  54 46 0  0 —  0  99 82  99100  92   99 27 100 100 83  55*  0*  0*  25*  0*  74*  99* 84  96* 100*99*  100*  41*  100*  100* 85  97 84 0 100  9 100  50 86  99 100* 99*100  99* 100 100 87 100  0* 100   99*  0*  99  99 88 —  0 0  99  0  68 89 89 —  0 0  93  0  89 100 90 — 100* 99*  100*  74*  100* 100 91 —  00 100  0  68  99 92 —  99* 94*  100*  74*  99*  100* 93  90 — —  7 —  91100 94  99 — — 100 — 100 100 95  94* — —  99* —  98*  95* 96  60*  0* 0*   0* —   0*  26* 97  99 — — 100 — 100  99 98  94* — —  100* —  100* 100* 99  97 — — 100 — 100  99 100 — — — 100 — 100  99 101 — — — 100 — 99  72 102  0 — —  0 —  55  97 103  99 — —  98 —  96  95 104   0* — — 98* —  97*  72* 105   0* — —  100* —  98*  81* 106  98 — — 100 —  97  0107   9* — —  99* —  99*  99* 108  99* — —  100* —  100*  100* 109   0*— —  100* —  98*  97* 110   0* — —  100* —  98*  99* 111 100 — — 100 —100 100 112  80 — — 100 — 100  97 113  99 — — 100 — 100 100 114  21 — —100 —  98  98 115  88* — —  100* —  94*  99* 116   0* — —  78* —   9*  0* 117 100 — — 100 — 100 100 118 100 — — 100 —  99 100 119 100 — — 100— 100 100 120 100 — — 100 — 100 100 121  97* — —  100* —  100*  100* 122 98* — —  100* —  100*  99* 123  87* — —  100* —  99*  90* 124  99 — —100 — 100 100 125  82 — — 100 — 100  87 126 100 — — 100 — 100 100 127 76 — — 100 —  91  99 128  43* —  0*  100* —  85*  56* 129 100 — — 100 — 99 100 130 100 — — 100 — 100 100 131  98 — — 100 — 100  98 132  0 — — 100* —  99* 100 133 100 — — 100 — 100  99 134 100 — — 100 — 100  99 135100 — — 100 — 100  99 136 100 — — 100 — 100 100 137 100 — — 100 — 100100 138  66* — —  16* —  55*  93* 139  83* — —  100* —  80*  96* 140 100* — 99*  100* —  99*  100* 141  100* — 97*  100* —  99*  99* 142 100* — 60*  100* —  100*  100* 143  100* —  0*  100* —  99*  98* 144 78* —  0*  100* —  100*  98* 145  26* —  0*  35* —  82*  73* 146  0 — — 18 —  17  0 147   0* — —   0* —  17*   0* 148 100 — — 100 — 100  99 149100 — — 100 — 100 100 150  8 — —  0 —  9  0 151  16 — —  0 —  99  43 152 100* — —  100* —  100*  100* 153  100* — —  100* —  100*  100* 154 100— — 100 — 100 100 155  99* — —  100* —  100*  99* 156  100* — —  100* — 99*  99* 157  100* — —  100* —  100*  100* 158  0 — —  8 —  0  13 159 0 — —  0 —  0  0 160  95* — —  100* —  100*  98* 161  94* — —  100* — 92*  90* 162  99* — —  100* —  86*  64* 163 100 — — 100 — 100  98 164100 — — 100 — 100  0 165 100 — — 100 — 100 100 166  99* — —  100* —  99* 93* 167   0* — —  58* —   0*   0* 168  21* — —  100* —  88*  100* 169  0* — —  68* —  88*   0* 170  100* — —  100* —  100*  98* 171  100* — — 100* —  100*  89* 172  99* — —  100* —  100*  100* 173  87* — —  100* — 100*  95*

What is claimed is:
 1. A compound selected from Formula I, N-oxides, andsalts thereof,

wherein Q¹ is a phenyl ring substituted with 1 to 5 substituentsindependently selected from R^(3a); Q² is a phenyl ring substituted with1 to 5 substituents independently selected from R^(3a); or a 5- to6-membered fully unsaturated heterocyclic ring, each ring containingring members selected from carbon atoms and 1 to 3 heteroatomsindependently selected from up to 2 O, up to 2 S and up to 3 N atoms,wherein up to 2 carbon ring members are independently selected fromC(═O) and C(═S), each ring optionally substituted with up to 5substituents independently selected from R^(3a) on carbon atom ringmembers and R^(3b) on nitrogen atom ring members; R¹ is C₁-C₂ alkyl,halomethyl, cyanomethyl or cyclopropyl; R² is H, halogen, cyano, C₁-C₂alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₂ haloalkyl, C₂-C₃ cyanoalkyl,C₁-C₂ hydroxyalkyl, cyclopropyl, halocyclopropyl, C₂-C₃ alkoxyalkyl,C₁-C₂ alkylthio, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy; each R^(3a) isindependently halogen, cyano, hydroxy, nitro, amino, C₁-C₃ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₁-C₃ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₄-C₆ alkylcycloalkyl, C₄-C₆ cycloalkylalkyl, C₁-C₃alkylthio, C₁-C₃ haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₃alkoxy, C₁-C₃ haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃ alkylsulfonyloxy,C₁-C₃ haloalkylsulfonyloxy, C₂-C₄ alkylcarbonyloxy, C₂-C₄ alkylcarbonyl,C₁-C₃ alkylamino, C₂-C₄ dialkylamino, C₂-C₄ alkylcarbonylamino, —CH(═O),—NHCH(═O), —SF₅, —SC≡N or -U—V-T; each R^(3b) is independently cyano,C₁-C₃ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₂-C₄alkoxyalkyl, C₂-C₄ alkylaminoalkyl, C₃-C₄ dialkylaminoalkyl, C₁-C₃alkoxy, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl; R⁴ is halogen, —OR⁷or —SC≡N; R⁵ is H or C₁-C₄ alkyl; R⁷ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ cyanoalkyl, C₂-C₆alkoxyalkyl, —CH(═O), —S(═O)₂OM¹ or —C(═W)R⁹; R⁹ is C₁-C₆ alkyl, C₂-C₆alkoxyalkyl, C₂-C₆ alkylaminoalkyl, C₃-C₆ dialkylaminoalkyl, C₂-C₆alkylthioalkyl, C₁-C₆ alkoxy or C₁-C₆ alkylthio; each U is independently0, S(═O)_(n), N(R¹⁰) or a direct bond; each V is independently C₁-C₆alkylene, C₂-C₆ alkenylene, C₃-C₆ alkynylene, C₃-C₆ cycloalkylene orC₃-C₆ cycloalkenylene, wherein up to 3 carbon atoms are independentlyselected from C(═O), each optionally substituted with up to 5substituents independently selected from halogen, cyano, nitro, hydroxy,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy; each Tis independently cyano, N(R^(11a))(R^(11b)), OR^(12 or S(═O)) _(n)R¹²;each R¹⁰ is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈cycloalkoxy(thiocarbonyl); each R^(11a) and R^(11b) is independently H,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl),C₄-C₈ cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or a pairof R^(11a) and R^(11b) are taken together with the nitrogen atom towhich they are attached to form a form a 3- to 6-membered heterocyclicring, the ring optionally substituted with up to 5 substituentsindependently selected from R¹³; each R¹² is independently H, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl,C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆(alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); each R¹³ isindependently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₁-C₆ alkoxy; Wis O or S; M¹ is K, Na or Li; and each n is independently 0, 1 or 2;provided that when Q² is a phenyl ring which is not substituted withR^(3a) at either ortho position, then Q¹ is substituted by at least oneR^(3a) at an ortho position.
 2. A compound of claim 1 wherein: Q¹ is aphenyl ring substituted with 1 to 3 substituents independently selectedfrom R^(3a); Q² is a phenyl ring substituted with 1 to 3 substituentsindependently selected from R^(3a); or a pyrazolyl, imidazolyl,pyridinyl, pyridazinyl, pyrazinyl or pyrimidinyl ring, each ringoptionally substituted with up to 3 substituents independently selectedfrom R^(3a) on carbon atom ring members and R^(3b) on nitrogen atom ringmembers; R¹ is C₁-C₂ alkyl, —CH₂F, —CH₂Cl or cyclopropyl; R² is H,halogen, cyano, C₁-C₂ alkyl, C₂-C₄ alkenyl, halomethyl, cyanomethyl,hydroxymethyl, C₂-C₃ alkoxyalkyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy; eachR^(3a) is independently halogen, cyano, C₁-C₂ alkyl, C₁-C₂ haloalkyl,cyclopropyl, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₂-C₃ alkylcarbonyl or—U—V-T; each R^(3b) is independently cyano, C₁-C₂ alkyl, cyclopropyl orC₂-C₃ alkoxyalkyl; R⁴ is Br, Cl, F, —OR⁷ or —SC≡N; R⁵ is H or methyl; R⁷is H, C₁-C₃ alkyl, C₂-C₆ alkenyl, C₁-C₃ haloalkyl, cyclopropyl, C₂-C₃cyanoalkyl, C₂-C₆ alkoxyalkyl, —S(═O)₂OM¹ or —C(═W)R⁹; R⁹ is methyl ormethoxy; each U is independently O, N(R¹⁰) or a direct bond; each R¹⁰ isindependently H or methyl; each V is independently C₁-C₃ alkylene,wherein up to 1 carbon atom is selected from C(═O); each T isindependently N(R^(11a))(R^(11b)b) or OR¹²; each R^(11a) and R^(11b) isindependently H or methyl; each R¹² is independently H, C₁-C₆ alkyl orC₁-C₆ haloalkyl; W is O; and M¹ is Na or K.
 3. A compound of claim 2wherein: Q² is a phenyl ring substituted with 1 to 3 substituentsindependently selected from R^(3a); or a pyrazolyl, imidazolyl orpyridinyl ring, each ring optionally substituted with 1 to 3substituents independently selected from R^(3a) on carbon atom ringmembers and R^(3b) on nitrogen atom ring members; R¹ is methyl, —CH₂F or—CH₂Cl; R² is halogen, cyano, C₁-C₂ alkyl, halomethyl, cyanomethyl,hydroxymethyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy; each R^(3a) isindependently halogen, cyano, methyl, halomethyl, cyclopropyl, methoxy,methylthio, methylcarbonyl or —U—V-T; each R^(3b) is methyl; R⁴ is Br,Cl, F or —OR⁷; R⁷ is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, —S(═O)₂OM¹ or—C(═W)R⁹; each U is independently O, NH or a direct bond; each V isC₁-C₃ alkylene; and each R¹² is independently H, methyl or halomethyl.4. A compound of claim 3 wherein: Q² is a phenyl ring substituted with 1to 3 substituents independently selected from R^(3a); R¹ is methyl; R²is halogen, cyano, methyl, halomethyl or methoxy; each R^(3a) isindependently halogen, cyano, methyl, halomethyl or methoxy; R⁴ is —OR⁷;R⁵ is H; R⁷ is H, methyl or —C(═W)R⁹; and R⁹ is methyl.
 5. A compound ofclaim 4 wherein: R² is Br, Cl, methyl or methoxy; each R^(3a) isindependently halogen, cyano or methoxy; and R⁷ is H.
 6. A compound ofclaim 5 wherein: R² methyl; each R^(3a) is independently Br, Cl, F,cyano or methoxy; and one of Q¹ and Q² is substituted with 2 to 3substituents and the other of Q¹ and Q² is substituted with 1 to 2substituents.
 7. The compound of claim 1 which is selected from thegroup:α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;(αS)-α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;(αR)-α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;α-(2-chloro-4-fluorophenyl)-5-(2,6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;(αS)-α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;(αR)-α-(2-chloro-4-fluorophenyl)-5-(2,6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;α,5-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;5-(2-bromophenyl)-α-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;α-(2-chloro-4-fluorophenyl)-5-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;α-(2-chloro-4-fluorophenyl)-1,3-dimethyl-5-(2,4,6-trifluorophenyl)-1H-pyrazole-4-methanol;α-(2-bromo-4-fluorophenyl)-5-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;α-(2-bromo-4-fluorophenyl)-5-(2-chloro-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;3-bromo-5-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;5-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;5-(2,4-dichlorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;5-(2-chloro-6-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;α-(2,4-difluorophenyl)-5-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;4-[4-[(2,4-difluorophenyl)hydroxymethyl]-1,3-dimethyl-1H-pyrazol-5-yl]-3,5-difluorobenzonitrile;5-(2-chloro-6-fluorophenyl)-α-(2,4-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;5-(2-chloro-6-fluorophenyl)-α-(2,6-dichlorophenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-α-(2,4,6-trifluorophenyl)-1H-pyrazole-4-methanol;5-(2-bromo-4-fluorophenyl)-1,3-dimethyl-α-(2,4,6-trifluorophenyl)-1H-pyrazole-4-methanol;5-(2-chloro-6-fluorophenyl)-α-(2-chloro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole-4-methanol;3-bromo-α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;3-chloro-α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;α-(2-chloro-4-fluorophenyl)-5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;α-(2-chloro-4-fluorophenyl)-5-(2-chloro-6-fluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;5-(2,6-difluorophenyl)-α-(4-fluoro-2-methylphenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;α-(2-chloro-4-methoxphenyl)-5-(2,6-difluorophenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;5-(2,6-difluorophenyl)-3-methoxy-α-(4-methoxy-2-methylphenyl)-1-methyl-1H-pyrazole-4-methanol;5-(2-chloro-6-fluorophenyl)-α-(2-chloro-4-methoxyphenyl)-3-methoxy-1-methyl-1H-pyrazole-4-methanol;3-chloro-5-(2,6-difluorophenyl)-α-(4-methoxy-2-methylphenyl)-1-methyl-1H-pyrazole-4-methanol;3-chloro-5-(2,6-difluorophenyl)-α-(2-fluoro-4-methoxyphenyl)-1-methyl-1H-pyrazole-4-methanol;3-chloro-α-(2-chloro-4-methoxyphenyl)-5-(2,6-difluorophenyl)-1-methyl-1H-pyrazole-4-methanol;and3-bromo-5-(2,6-difluorophenyl)-α-(4-methoxy-2-methylphenyl)-1-methyl-1H-pyrazole-4-methanol.8. A fungicidal composition comprising (a) a compound of claim 1; and(b) at least one other fungicide.
 9. A fungicidal composition comprising(a) a compound of claim 1; and (b) at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents.
 10. A method for controlling plant diseases caused byfungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of claim 1.